Syngenta Limited, a corporation organized and existing under the laws of United
Kingdom, of European Regional Centre, Priestley Road, Surrey Research Park, Guildford,
Surrey GU2 7YH United Kingdom.
And
Syngenta Participations AG, a corporation organized and existing under the laws of
Swiberland, of Schwarzwaldallee 215, CH-4058 Basel, Switzerland.
The following specification particularly describes the nature of this invention and the manner
in which it is to be performed:
HERBICIDAL COMPOUNDS
The present invention relates to heterocyclic sulphonamide derivatives, to
processes and intermediates for making these compounds, to herbicidal compositions
comprising these compounds, and to methods of using these compounds to control
plant growth.
WO 20091063180 A1 (Syngenta Limited) and WO 201 111 17151 (BASF SE) both
disclose certain herbicidal pyridine sulphonamide derivatives.
W020101130970 (Syngenta Limited) discloses certain 6,6-dioxo-6-thia-I ,4-
diaza-naphthalene derivatives having herbicidal properties.
It has now surprisingly been found that certain heterocyclic sulphonamides have
herbicidal andlor plant-growth-inhibiting properties.
The present invention therefore provides a compound of formula (I)
wherein
A', A', and A3 are independently C-R' or N, provided at least one of A', A', and A3 is N;
each R1 i-s .~ ndependentlyh ydrogen, C1-C4alkyl,C ,-C, alkenyl, Cl-C4 alkynyl, C1-
C4haloalkyl, C3-C6cycloalkyl, halo, cyano, hydroxy, C,-C4alkoxy, C02R2, C(0)R2
where R2 is hydrogen or C1-C6 alkyl, C1-C4alkylthio, aryl or aryl substituted by
one to five Rkroups which may be the same or different, or heteroaryl or
heteroaryl substituted by one to five R@groups which may be the same or
different;
R is hydrogen, hydroxy, OR5, thiol (HS-), C1-C3alkylthio-, Clfluoroalkylthio-. Cl-C3alkyl-
S(0)-, C~fluoroalkyl-S(0)-C, 1-C3alkyl-S(0)2-C, lfluoroalkyl-S(O),-, H2N-S(0)2-,C 1-
C4alkyl-NH-S(O),-, (C,-C3alkyl)2N-S(0)2-, halo, cyano, C1-C4alkyl, Cl-C2haloalkyl or C,-
C4alkoxy and N R ' w~h~er ein each R 'i~s in dependently selected from the group
hydrogen, Cl.4alkyl, S 0 2 ~ "p, henyl and phenyl which is mono or poly-substituted with
R ~ ;
R3 is hydrogen, Cl-Cloalkyl, C1-C4haloalkyl.C 2-Cloalkenyl, C2-C4haloalkenyl,C 2-
Cloalkynyl, C2-c4haloalkyny1, C3-Clocycloalkyl, C3-C1o~y~l0alkyl-C1-C~alkyClI--,
Cloalkoxy-C1-C6alkyl-, C1-Clocyanoalkyl-, CI-C,oalkoxycarbonyl-Cl-CGalkyl-, N-C1-
C3alkyl-aminocarbonyl-C1-Csalkyl-N, ,N-di-(C1-C3alkyl)-aminocarbonyl-C1-C6alkyla-,w l-
C1-C~alkylo- r awl-C1-CGalkylw- herein the aryl moiety is substituted by one to three R7,
which may be the same or different, or heterocyclyl-Cl-CGalkyl-, wherein the heterocyclyl
moiety is substituted by one to three R7groups, which may be the same or different; or
R3 is R4 of sub-formula (a);
R~ is of sub-formula (a) or (b):
wherein, in sub-formula (a):
R ~ ~ ,R ~R~~~a ,nd R~~a re each independently hydrogen, halogen, cyano, C1-C,alkyl,
C1-Czfluoroalkyl, Cl-C3alkoxy-Cl-C2alkyl-, Clfluoroalkoxy-C1-C2alkyl-,
MeOCH2CH20CH2-C, 3-C6cycloalkyl,h ydroxy, C1-C4alkoxy,C 1-Czfluoroalkoxy,t hiol (HS-
), C1-C3alkylthio-, Clfluoroalkylthio-, C1-C3alkyl-S(0)-, Clfluoroalkyl-S(0)-. Cl-C3alkyl-
S(O)2-, Clfluoroalkyl-S(O)Z-,H zN-S(O)Z-,C 1-C4alkyl-NH-S(0)2-,( C1-C3alkyl)2N-S(0)2--,
S(0)2-OC1-C4alkyl.- S(0)2-OC1-C2fluoroaIkyl.C 1-C4alkyl-C(0)-,H -C(0)-, C1-C3alkoxy-
C(0)-, HO-C(0)-, H2N-C(0)-, C1-C4alkyl-NH-C(0)-,( C1-C3alkyl)2N-C(0)-(,I -pyrrolidiny1)-
C(0)-, (I-piperidiny1)-C(0)-, amino, Cl-C4alkyl-NH-, (C1-C3alkyl)2N-I,- pyrrolidinyl,
I-piperidinyl, Cl-C,alkyl-C(0)-NH-, H-C(0)-NH-, C1-C3alkyl-C(0)-N(C1-C3alkyl)-,
2-0x0-I-pyrrolidinyl, 2-0x0-I-piperidinyl, C1-C3alkyl-S(O)2-NH-C, 1-C3alkyl-S(0)2-N(C1-
C3alkyl)-, phenyl or phenyl substituted by one, two or three of R7, or phenoxy or phenoxy
substituted by one, two or three of R7;
and wherein, in sub-formula (b):
A5 is N or C R ~A~6 ,is N or C R ~ ~i,s N or C R ~A~' i,s N or CR4', and Agis N or CR4I,
provided that one or two of As, A', A7, A8 and A' are nitrogen and the remaining ones of
A5, A', A7, A' and A' are not nitrogen;
R"', R4g,R ~R4~'a n,d R4' are each independently hydrogen, halogen, C1-C4alkyl,C 1-
Cdluoroalkyl, C1-C3alkoxy-methyl-, Clfluoroalkoxy-methyl-, MeOCH2CH20CH2-, C3-
C6cycloalkyl, hydroxy (inclusive of any tautomer thereof), C,-C4alkoxy, Cl-
C2fluoroalkoxy, Cl-C4alkyl-C(0)-, H-C(0)-, Cl-C3alkoxy-C(0)-, HO-C(0)-, H2N-C(0)-, C1-
C4alkyl-NH-C(0)-, (Cl-C3alkyl)2N-C(0)-, (I-pyrrolidiny1)-C(0)-, (1-piperidiny1)-C(0)-,
amino, C1-C4alkyl-NH-, (C,-C3alkyl)2N-, I-pyrrolidinyl, I-piperidinyl, C,-C4alkyl-C(0)-NH-,
H-C(0)-NH-, C1-C3alkyl-C(0)-N(Cl-Csalkyl)-, 2-0x0-I-pyrrolidinyl, 2-0x0-I-piperidinyl,
phenyl or phenyl substituted by one, two or three of R8, or phenoxy or phenoxy
substituted by one, two or three of R8; or
R4' together with R4' may form a pyridine ring which is mono or poly-substituted with R4Q
as defined above; or
R~~ together with R4' may form a five to ten membered saturated or partially unsaturated
mono- or bicyclic ring containing 1 to 3 heteroatoms selected from the group consisting
of N, S and 0 which may be unsubstituted or mono or poly-substituted with R4Qa s
defined above; or
R5 is hydroxy, R9-oxy-, R'O-~(0)-0-C, ,-Cloalkyl-S(0)20-, Clfluoroalkyl-S(0)20-,
Clchloroalkyl-S(0)20-, phenyl-S(0)20- or (4-methyl-phenyl)-S(O)&-;
each R6 and each R7 are independently halo, cyano, nitro, C,-Cloalkyl, CT-C4haloalkyl,
C2-Cloalkenyl, C,-Cloalkynyl, hydroxy, C,-Cloalkoxy, Cl-C4haloalkoxy. C,-C~~alkoxy-Cl-
C4alkyl-. C3-C7cycloalkyl,C 3-C,cycloalkoxy, C3-C7cycloalkyl-C,-C4alkyl-,C 3-C7cycloalkyl-
C1-C4alkoxy-, C1-C6alkylcarbonyl-, formyl, C1-C4alkoxycarbonyl-, Cl-C4alkylcarbonyloxy-,
C1-Cloalkylthio-, C1-C4haloalkylthio-,C 1-Cloalkylsulfinyl-, C1-C4haloalkylsulfinyl-C, 1-
Cloalkylsulfonyl-, C1-C4haloalkylsulfonyl-a, mino, C1-Cloalkylamino-, di-Cl-Cloalkylamino-
, Cl-Cloalkylcarbonylamino-, aryl or aryl substituted by one to three RT2w, hich may be
the same or different, heteroaryl or heteroaryl substituted by one to three R1', which may
be the same or different, atyl-C,-C4alkyl- or aryl-C,-C4alkyl- wherein the aryl moiety is
substituted by one to three R", which may be the same or different, heteroaryl-Cl-
C4alkyl- or heteroaryl-C1-C4alkyI-w herein the heteroaryl moiety is substituted by one to
three R", which may be the same or different, aryloxy- or aryloxy- substituted by one to
three R12, which may be the same or different, heteroatyloxy- or heteroaryloxysubstituted
by one to three Rq2w, hich may be the same or different, arylthio- or arylthiosubstituted
by one to three R", which may be the same or different, or heteroarylthio- or
heteroarylthio- substituted by one to three R", which may be the same or different;
each R' is independently, fluorine, chlorine, Cl-C~alkyl, Clfluoroalkyl, C,-C2alkoxy or
Clfluoroalkoxy;
R9 is C1-Cloalkyl, C,-C4fluoroalkyl, Cz-Cl0alkenyl, C2-Cl0alkynyl, C3-C~cycloalkyCl, SC8cycloalkyl-
C,-C4alkyl-, C1-C,alkoxy-CH2CH2-, C,-C4alkoxy-CH2CH2CH2-, phenyl-C1-
C4alkyl-, or phenyl-C,-C4alkyl- wherein the phenyl moiety is substituted by one, two or
three R";
R" is C1-Cloalkyl, C1-C4fluoroalkyl, C2-C,oalkenyl, C2-Cloalkynyl, C3-C8cycloalkyl, C3-
Cscycloalkyl-C1-C4alkyl-,C 1-C4alkoxy-C1-C4alkyl-,p henyl, phenyl substituted by one, two
or three R", phenyl-C,-C4alkyl-, or phenyl-C1-C4alkyl- wherein the phenyl moiety is
substituted by one, two or three R";
each R$ 1 .1s .~ ndependentlyh alo, C,-C4alkyl, C1 C2fluoroalkyl, C,-C4alkoxy, C,
Czfluoroalkoxy, phenyl or phenyl substituted with R7;
each R" is independently halo, cyano, nitro, C,-C6alkyl, C,-C6haloalkyl or Cl-C,alkoxy;
or a salt or N-oxide thereof
In the description and claims of this specification, when references are made to a
compound of formula (I), or to a compound of the invention, or to a compound (which is
implicitly a compound of formula (I) or a compound of the invention), these references
are intended to encompass the compound or a salt (e.g. agriculturally acceptable salt)
thereof.
The compounds of formula (I) may exist in different geometric or optical isomers
or tautomeric forms. The present invention covers all such isomers and tautomers and
mixtures thereof in all proportions. Furthermore, it is possible that atropisomers are
obtained in those cases where the rotation of the R4 group is restricted, for example in
those cases where the R4 group (e.g. of sub-formula (a)) has at least one orthosubstituent,
and all such atropisomers are included in the invention.
As an example of tautomerism, a compound of formula (la), i.e. a compound of
formula (I) where R5 is hydroxy, can be drawn in two tautomeric forms illustrated below,
and the present invention covers each of these tautomeric forms as well as a mixture of
these two tautomeric forms.
Alkyl groups (either alone or as part of a larger group, such as alkoxy, alkoxycarbonyl-,
alkylcarbonyl-, et al.) can be in the form of a straight or branched chain.
Typical examples are methyl, ethyl, propan-I-yl (n-propyl or propyl), propan-2-yl
(isopropyl or I-methylethyl), butan-I-yl (n-butyl or butyl), butan-2-yl (sec-butyl or 1-
methylpropyl), 2-methylpropan-I-yl (isobutyl or 2-methylpropyl), or 2-methylpropan-2-yl
(tert-butyl or I ,I-dimethylethyl). Except where more narrow ranges are stated, in
general, alkyl groups are preferably C1-C6 alkyl, more preferably C,-C4 alkyl, most
preferably C1-C3 alkyl groups.
Alkenyl groups (either alone or as part of a larger group, such as alkenyloxy) can
be in the form of a straight or branched chain, and can be, where appropriate, of either
the (E)- or (Z)-configuration. Typical examples are vinyl, allyl (prop-2-enyl) or 3-methylbut-
2-enyl. Except where more narrow ranges are stated, in general, alkenyl groups are
preferably CZ-C6, more preferably C2-C4, most preferably CZ-C3 alkenyl groups.
Alkynyl groups (either alone or as part of a larger group, such as alkynyloxy) can
be in the form of a straight or branched chain. Typical examples are ethynyl, propargyl
(prop-2-ynyl) or but-2-ynyl. Except where more narrow ranges are stated, in general,
alkynyl groups are preferably C2-CGm, ore preferably C2-C4,m ost preferably C2-C3
alkynyl groups.
Halogen is fluorine, chlorine, bromine or iodine. Preferably, e.g. in the
compound of formula (I), halogen is fluorine, chlorine or bromine; such as fluorine or
chlorine.
Fluoroalkyl groups (either alone or as part of a larger group, such as fluoroalkoxy
or fluoroalkylthio-) are alkyl groups (straight-chain or branched) which are substituted by
one or more (e.g. 1, 2 or 3) fluorine atoms. Typical examples are trifluoromethyl (CF3),
difluoromethyl, monofluoromethyl, 2,2,2-trifluoro-ethyl, 2,2-difluoro-ethyl (CHF2CH,-),
2-fluoro-ethyl or perfluorobutan-I-yl; in particular trifluoromethyl or 2,2,2-trifluoro-ethyl.
Typical examples of fluoroalkoxy groups are difluoromethoxy, trifluoromethoxy,
monofluoromethoxy, 2,2,2-trifluoro-ethoxy, 2,2-difluoro-ethoxy or 2-fluoro-ethoxy; in
particular difluoromethoxy (CHF20).
Chloroalkyl groups (either alone or as part of a larger group, such as
chloroalkoxy or chloroalkylthio-) are alkyl groups (straight-chain or branched) which are
substituted by one or more (e.g. 1, 2 or 3) chlorine atoms. Typical examples are
dichloromethyl, trichloromethyl or monochloromethyl, 2,2,2-trichloro-ethyl, 2,2-dichloro..
ethyl, or 2-chloroethyl.
Fluoroalkenyl and chloroalkenyl groups are alkenyl groups which are substituted
by one or more (e.g. 1, 2 or 3) fluorine or chlorine atoms respectively. Typical examples
of fluoroalkenyl are I-fluorovinyl, 2,2-difluoro-vinyl or 1,2,2-trifluoro-vinyl. Typical
examples of chloroalkenyl are I-chlorovinyl, 1,2-dichloro-vinyl, 2,2-dichloro-vinyl or
1,2,2-trichloro-vinyl.
Fluoroalkynyl and chloroalkynyl groups are alkynyl groups which are substituted
by one or more (e.g. 1, 2 or 3) fluorine or chlorine atoms respectively. Typical examples
of fluoroalkenyl are 1-fluoro-prop-2-ynyl, I ,I-difluoro-prop-2-ynyl or 3-fluoro-prop-2-ynyl.
Typical examples of chloroalkynyl are I-chloro-prop-2-ynyl or 3-chloro-prop-2-ynyl.
Cycloalkyl groups (either alone or as part of a larger group, such as cycloalkylalkyl-)
are monocyclic carbocycles. Typical examples are cyclopropyl, cyclobutyl,
cyclopentyl or cyclohexyl. Except where more narrow ranges are stated, in general,
cycloalkyl groups are preferably C3-C6, more preferably C,-C, cycloalkyl groups, most
preferably Cscycloalkyl, i.e., cyclopropyl.
Heterocyclyl groups (either alone or as part of a larger group, such as
heterocyclyl-alkyl-) are monocyclic saturated ring systems containing at least one ring
heteroatom. Preferably, heterocyclyl groups will have one or two ring heteroatoms
selected from nitrogen, oxygen and sulfur. Typical examples of heterocyclic groups
include oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, azetidinyl, pyrrolidinyl, piperidinyl,
piperazinyl, morpholinyl, or thietanyl. Heterocyclyl groups having a single oxygen or
nitrogen atom as the ring heteroatom are preferred. Except where more narrow ranges
are stated, in general, heterocyclyl groups are preferably 4-, 5- or 6-membered rings,
more preferably 5- or 6-membered rings.
Aryl groups (either alone or as part of a larger group, such as aryloxy- or
arylthio-) are monocyclic or fused bicyclic aromatic ring systems. Examples of such rings
include phenyl, naphthyl, or indenyl. The preferred aryl group is phenyl.
Heteroaryl groups (either alone or as part of a larger group, such as
heteroaryloxy- or heteroarylthio-) are monocyclic or fused bicyclic aromatic ring systems
containing at least one ring heteroatom. Preferably, single rings will have one, two or
three heteroatoms selected from nitrogen, oxygen and sulfur. Typical examples of
monocyclic heteroaryl groups are pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl,
pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thiophenyl, oxazolyl,
isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl or thiadiazolyl. Preferably, bicyclic systems
will have one, two, three or four ring heteroatoms selected from nitrogen, oxygen and
sulfur. Typical examples of bicyclic heteroatyl groups are quinolinyl, cinnolinyl,
quinoxalinyl, indolyl, indazolyl, benzimidazolyl, benzothiophenyl or benzothiadiazolyl.
Monocyclic heteroatyl groups are preferred, and pyridyl is generally most preferred.
Where R5 is other than hydroxy, the R~ group is in most cases intended to be
metabolised by a plant to a hydroxy group. In some cases, a R5 group, which is other
than hydroxy, might increase penetration of the compound of formula (I) into a plant, e.g.
might increase penetration across the cuticule of the leaf of a plant, before metabolism
by the plant of the R5 group to a hydroxy group. Plant metabolism means the
conversion or breakdown of a substance from one form to another by a plant (in planta).
Salts comprise a charged version of a compound of formula (I) and a counter ion
of the opposite charge. The salt is preferably agriculturally acceptable. The compounds
of formula (I) can have a negative charge, for example, on an oxygen atom of a hydroxy
group, if the hydroxy group is deprotonated witha base (e.g. ammonia or an alkali metal
hydroxide). Suitable cationic counter ions include, for example, alkali metals such as
sodium or potassium, or alkaline earth metals such as magnesium or calcium, or
quaternary ammonium such as ammonium or tetramethylammonium. Alternatively, the
compounds of formula (I) can have a positive charge, for example, on the nitrogen atom
in a nitrogen-containing heteroaryl group; for example: if the nitrogen atom is
quaternised by protonation with an organic or inorganic acid, or if the nitrogen atom is
quaternised by alkylation for example with a methyl group, or if the nitrogen atom is
quaternised by amination. Suitable anionic counter ions include, for example, an anion
of an organic acid, or an inorganic anion such as hydroxide, fluoride, chloride, bromide,
iodide, sulfate, phosphate or nitrate.
The compounds of formula (I) according to the invention (encompassing a
compound or a salt thereof) also include hydrates, which, for example, may be formed
during salt formation.
Preferred, particular, suitable, typical or optional values of A', A', A3, A5, A6, A7,
A8, A', R, R', R2, R3,R 4,R4aR, ~R4~c,R , ~R~~R,~~ R,~4g ,,R ~R~~R,~4j ,, R 5, R6, R7, R', RO,
R", R", R", RT3 ef a/., are as set out below, and these preferred features can be taken
together in any combination.
Up to all three of A', A2, and A3 can be N. Preferably up to two of A', A2, and A3
are N. More preferably, only one of A', A2, orA3 is N. Most preferably only A3 is N.
Preferably R is hydrogen, OR5, thiol (HS-), C,.,alkylthio, halo, cyano and NR132.
Preferably each R' is independently hydrogen, C,-C4alkyl, C1-C4haloalkyl,h alo,
cyano, hydroxyl, C1-C4alkoxy, C02R2 or C(0)R2. More preferably each R' is hydrogen,
C1-C4alkyl, halo, cyano, hydroxy, COOH, or C(0)Me. More preferably still, each R' is
independently hydrogen, C1-C4alkyl, halo, cyano or hydroxy, Even more preferably
each R' is independently hydrogen, methyl, chloro or bromo. Yet even more preferably
each R' is independently hydrogen or chloro. Most preferably each R' is hydrogen.
Preferably R2 is H or C1-C4 alkyl. More preferably R2 is H or methyl.
Preferably R3 is hydrogen, Cl-C4alkyl, C1-C,haloalkyl, C2-C4alkenyl, CZC4haloalkenyl,
C2-C4alkynyl, C1-Cloalkoxy-Cl-C6alkyl- or C2-C4haloalkynyl. Examples of
such preferred groups for R3 are hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-
methyl-propyl, 2-fluoro-ethyl, 2,2-difluoro-ethyl, 2,2,2-trifluoro-ethyl, allyl, but-3-en-I-yl,
methoxymethyl, or propargyl.
More preferably R3 is hydrogen, Cl-C2alkyl, Cl-C2haloalkyl, C2-C3alkenyl, C1-
Cloalkoxy-C1-C6alkyl- or C2-C3alkynyl. Examples of such more preferred groups for R3
are hydrogen, methyl, ethyl, 2,2-difluoro-ethyl, 2,2,2-trifluoro-ethyl, allyl, methoxymethyl
or propargyl.
Most preferably R3 is hydrogen, Cl-C~alkyl, C1-C2haloalkyl, C,-Cloalkoxy-Cl-
C~alkylo- r C2-C,alkynyl. Examples of such most preferred groups for R3 are hydrogen,
methyl, ethyl, 2,2-difluoro-ethyl, methoxymethyl or propargyl. In one preferred
embodiment R3 is 2,2-difluoro-ethyl.
In R4, sub-formula (a), preferable features are as follows.
Preferably, no more than one of R ~ a~n,d R4di s C3-C6cycloalkyl,( 1-
pyrrolidiny1)-C(0)-, (I-piperidiny1)-C(0)-, I-pyrrolidinyl, I-piperidinyl, 2-0x0-I-pyrrolidinyl,
2-0x0-I-piperidinyl, phenyl, substituted phenyl, phenoxy or substituted phenoxy.
Preferably, R4a,R ~R~~R,~~ ~a, n d Re are independently hydrogen, halogen
(fluorine, chlorine, bromine or iodine). C1-C4alkyl (e.g. methyl or ethyl), C,fluoroalkyl (e.g.
CF3), methoxymethyl-, MeOCH2CH20CH2-, C3-Cscycloalkyl (e.g. cyclopropyl), C1-
C3alkoxy (e.g. methoxy or ethoxy), C,fluoroalkoxy (such as CHF20, CF30 or CH2F0, in
particular CHF20), Cl-C~alkyl-S(O),- (e.g, methyl-S(0)2-), H2N-S(0)2-, C1-
C3alkyl-NH-S(0)2-( e.g. MeNH-S(0)2-), (C1-C3alkyl)2N-S(0)2(-e .g. Me2N-S(O)>-),p henyl
or phenyl substituted by one or two of R7, wherein each R7, independently of any other
R7, is fluorine, chlorine, methyl, Clfluoroalkyl (e.g. CF,), methoxy or Clfluoroalkoxy (e.g.
CHF20, CF30 or CH2F0, in particular CHF20).
More preferably, R4=,R ~R~~R,~~ ~a ,nd R~~a re independently hydrogen, fluorine,
chlorine, bromine, methyl, ethyl, Clfluoroalkyl (e.g. CF3), cyclopropyl, methoxy, ethoxy,
C,fluoroalkoxy (such as CHF20, CF30 or CH2F0, in particular CHF20), or methyl-S(0)2;
or phenyl or phenyl substituted by one or two (e.g. one) of R7, wherein each R7,
independently of any other R7, is fluorine, chlorine, methyl, CF,, methoxy, CHF20 or
CH2F0.
Still more preferably, R ~R~~R,4~' , R,~ ~a nd R~~a re independently hydrogen,
fluorine, chlorine, bromine, methyl, ethyl. C,fluoroalkyl (e.g. CF,), cyclopropyl, methoxy,
Clfluoroalkoxy (such as CHF20, CF,O or CH2F0, in particular CHF20), or
methyl-S(0)2-.
Preferably, in these cases, at least one of R~~ and R4e is not hydrogen or fluorine.
Most preferably, R4a is chlorine or CF3; in which case R~~ is preferably hydrogen,
fluorine, chlorine, bromine, methyl, CF, or methoxy.
Preferably, one or two (e.g. two) of R ~R4~' a,nd R~~a re hydrogen.
Preferably, in R4 sub-formula (a) or (b), R7, independently of any other R7, is
fluorine, chlorine, methyl, C,fluoroalkyl (e.g. CF,), methoxy or C,fluoroalkoxy (e.g.
CHF20, CFjO or CH2F0, in particular CHF20).
In one particular embodiment R4 is 2-trifluoromethyl-phenyl-.
In one particular embodiment R4 is 2-chloro-phenyl-.
In one particular embodiment R4 is 2-bromo-phenyl-.
In one particular embodiment R4 is 2-methyl-phenyl-.
In one particular embodiment R4 is 2-methoxy-phenyl-.
In one particular embodiment R4 is 2,4-difluoro-phenyl-.
In one particular embodiment R4 is 2,6-dichloro-phenyl-.
In one particular embodiment R4 is 2,3-dichloro-6-fluoro-phenyl-.
In one particular embodiment R4 is 2-chlor0-3,6-difluoro-phenyl-.
In one particular embodiment R~ is 3-bromo-2-~hlor0-6-fluoro-phenyl-.
In one particular embodiment R4 is 2,3,6-trichloro-phenyl-.
In one particular embodiment R4 is 2-chloro-5-trifluoromethyl-phenyl-.
In one particular embodiment R4 is 2-chloro-6-trifluoromethyl-phenyl-.
In one particular embodiment R4 is 2,5-bis-(trifluoromethyl)-phenyl-.
In one particular embodiment R4 is 2-bromo-5-chloro-phenyl-.
In one particular embodiment R4 is 4-bromo-2-trifluoromethyl-phenyl-.
In one particular embodiment R4 is 4-chloro-2-methylsulfonyl-phenyl-.
In one particular embodiment R4 is 4-chloro-2-trifluorornethyl-phenyl-.
In one particular embodiment R4 is 5-chloro-2-trifluoromethyl-phenyl-.
In one particular embodiment R4 is 3,5-difluoro-2-trifluoromethyl-phenyl-.
In one particular embodiment R4 is 2-ethyl-4-(41-chloro-phenyl)-phenyl-.
In one particular embodiment R4 is 2,4,6-trimethyl-phenyl-.
In one embodiment R4 is 4-chloro-phenyl-.
In one embodiment R4 is 3-trifluoromethyl-phenyl-.
In one embodiment R4 is 4-fluoro-2-trifluoromethyl-phenyl-.
In one embodiment R4 is 5-fluoro-2-trifluoromethyl-phenyl-.
In one embodiment R4 is 2,4-dichloro-phenyl-.
In one embodiment R4 is 2-chloro-3,6-difluoro-phenyl.
In R4, sub-formula (b), the preferred features are as follows. Preferably, one of
A5, A', A', A8 and A' is nitrogen and the remaining ones of A5, A', A7, A8 and A' are not
nitrogen i.e. R4 is preferably pyridinyl or substituted pyridinyl.
In one particular embodiment, A5 is nitrogen and A', A7, A' and A' are not
nitrogen, thus giving an R4 that is a pyridin-2-yl or substituted pyridin-2-yl group.
In one particular embodiment, A' is nitrogen and A5, A7, A8 and A9 are not
nitrogen, thus giving an R4 that is a pyridin-3-yl or substituted pyridin-3-yl group
In one particular embodiment, A7 is nitrogen and A5, A6, A8 and A' are not
nitrogen thus giving an R4 that is a pyridin-4-yl or substituted pyridin-4-yl group.
Preferably no more than one of, R4g, R~~ and R4' is C3-C~cycloalkyl,
(1-pyrrolidiny1)-C(0)-, (I-piperidiny1)-C(0)-, I-pyrrolidinyl, I-piperidinyl,
2-0x0-I-pyrrolidinyl, 2-0x0-I-piperidinyl, phenyl, substituted phenyl, phenoxy or
substituted phenoxy.
Preferably, R4', R4g,R ~R~~~a n,d R4' are independently hydrogen, fluorine,
chlorine, Cl-C4alkyl (e.g. methyl or ethyl), C,fluoroalkyl (e.g. CF,), methoxymethyl-,
MeOCH2CH20CH2-, C3-C5cycloalkyl (e.g, cyclopropyl), hydroxy (inclusive of any
tautomer thereof); C,-C3alkoxy (e.g. methoxy or ethoxy), or C,fluoroalkoxy (such as
CHF20, CFjO or CH2F0, in particular CHF20); or phenyl or phenyl substituted by one,
two or three of Re, wherein each R' is independently fluorine, chlorine, methyl,
C,fluoroalkyl (e.g. CFs), methoxy or Clfluoroalkoxy (e.g. CHF20, CF30 or CH2F0, in
particular CHF,O).
More preferably, R4' and R ~a'r e independently hydrogen, fluorine, chlorine,
methyl or C,fluoroalkyl (e.g. CF3). Still more preferably, R4' and R4' are independently
hydrogen, chlorine or CF,. Preferably, in these cases, at least one of R4'and R4' is not
hydrogen or fluorine.
More preferably, one of R4' and R4' is chlorine. In this case, preferably, the other
of R4'and R4' is hydrogen, fluorine, chlorine, methyl, C,fluoroalkyl (e.g. CF3), or hydroxy
(inclusive of any tautomer thereof); or more preferably the other of R4' and R4' is
hydrogen, fluorine, chlorine, methyl or Clfluoroalkyl (e.g. CF,); or still more preferably
the other of R4' and R4' is hydrogen, chlorine or CF,.
More preferably, R4!', R~~ and R~~ are independently hydrogen, fluorine, chlorine,
methyl, or Clfluoroalkyl (e.g. CF,).
Preferably, one or two (e.g. two) of R ~R~~a ,nd R4'a re hydrogen.
When R4' is taken together with R4' forming a pyridine ring, sub formula (b) is
preferably:
When R~~ is taken together with R ~fo'r ming a five to ten membered saturated or
partially unsaturated mono- or bicyclic ring as defined above, sub formula (b) is preferably:
In some embodiments preferred examples of groups for R~ are 3,5-dichloropyridin-
2.~1, 3,6-dichloro-pyridin-2-yl, 3-chloro-5-fluoro-pyridin-2-yl, 3-chloro-5-
trifluoromethyl-pyridin-2-yl, 3,5,6-trichloro-pyridin-2-yl, 2,4-dichloro-pyridin-3-yl, 2,5-
dichloro-pyridin-3-yl, 2,6-dichloro-pyridin-3-yl, 4,6-dichloro-pyridin-3-yl, 2-chloro-4-
trifluoromethyl-pyridin-3-yl, 2-chloro-6-trifluoromethyl-pyridin-3.~1, 2-hydroxy-pyridin-3-yl
(inclusive of its pyridone tautomer), 2,3-dichloro-pyridin-4-yl, 2,5-dichloro-pyridin-4-yl,
3,5-dichloro-pyridin-4.~1, 3-chloro-5-trifluoromethyl-pyridin-4-yl, 2,3,5-trichloro-pyridin-4-
yl, or 5-chloro-pyrimidin-4-yl.
In further embodiments preferred examples of groups for R4 are 6-hydroxypyridin-
2-yl, 6-hydroxy-pyridin-3.~1, or 2-hydroxy-pyridin-4-yl (all inclusive of their
pyridone tautorners).
When R5 is Cl-Cloalkyl-S(0)20-, Clfl~~r~alkyl-S(0)2C0-1,~ hlor~alkyl-S(0)20-1
phenyl-S(0)20- or (4-methyl-phenyl)-S(0)20-, then it can for example be
methanesulfonyloxy-, ethanesulfonyloxy-, trifluorornethanesulfonyloxy-,
trichlorornethanesulfonyloxy-, benzenesulfonyloxy- or para-toluenesulfonyloxy-.
Preferably, R5 is hydroxy, ~ ~ - o xoyr -R 'O-~(0)-0.. More preferably, R5 is hydroxy
or R'O-C(0)-0-.
Preferably R6 and R7 are each independently halo, C,-C4alkyl, C1-C4haloalkyl,
Cl-C4alkoxy or Cl-C4haloalkoxy. Examples of such preferred groups for R~ are chloro,
fluoro, methyl, ethyl, trifluoromethyl, methoxy or trifluoromethoxy.
Most preferably each R~ is independently halo, C,-C4alkyl, C,-C4haloalkyl or C1-
C4alkoxy. Examples of such preferred groups for R7 are chloro, fluoro, methyl, ethyl,
trifluoromethyl and methoxy.
Preferably, R9 is C1-Csalkyl (e.g. C,-C6alkyl, such as C1-C4alkyl), Cl-
C2fluoroalkyl, C2-CSalkenyl-CH2(-e .g. allyl), C2-C5alkynyl-CH2(-e .g. propargyl), C3-
CGcycloalkyl,C 3-C,cycloalkyl-Cl-C2alkyl-, C1-C2alkoxy-CH2CH2-C, l-C2alkoxy-
CH2CH2CH2-, phenyl-C1-C2alkyl-, or phenyl-C1-C2alkyl- wherein the phenyl moiety is
substituted by one or two R"; and wherein each R" is preferably independently fluorine,
chlorine, Cl-C~alkyl, Clfluoroalkyl, Cl-C2alkoxy or Clfluoroalkoxy.
In one particular embodiment, R5 is R9-oxY- and is: methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, tea-butoxy, allyloxy, propargyloxy or benzyloxy.
Preferably, RIO is C1-Csalkyl (e.g. C,-CGalkyl, such as C2-C4alkyl, e.g. isopropyl or
terf-butyl), C1-C~fluoroalky(le .g. Clfluoroalkyl), C2-C~alkenylC, 2-C6alkynyl,C 3-
C~cycloalkylC, 3-CGcycloalkyl-C,-C2alkyl-C, ,-C2alkoxy-CH2-, C,-C2alkoxy-CH2CH2-,C 1-
C2alkoxy-CH2CH2CH2-p, henyl-C1-C2alkyl-,o r phenyl-C1-C~alkywl- herein the phenyl
moiety is substituted by one or two R1'; and wherein each R" is independently fluorine,
chlorine, methyl, ethyl, C,fluoroalkyl (e.g. trifluoromethyl), methoxy or C,fluoroalkoxy
(e.g. difluoromethoxy or trifluoromethoxy).
More preferably, R'O is C1-C8alkyl (in particular C1-C6alkyl, such as C2-C4alkyl,
e.g. isopropyl or terf-butyl).
Most preferably, RIO is C1-Csalkyl( in particular C1-C~alkyls,u ch as C2-C4alkyl,
e.g. isopropyl or terf-butyl).
In one particularly preferred embodiment, R5 is R'O-C(0)-0- and is: propan-2-
ylcarbonyloxy- (isopropylcarbonyloxy-), 2-methyl-propan-2-ylcarbonyloxy- (terfIn
one even more particularly preferred embodiment, R5 is R'O-C(0)-0- and is:
propan-2-ylcarbonyloxy- (isopropylcarbonyloxy-) or 2-methyl-propan-2-ylcarbonyloxy-
(tert-butylcarbonyloxy-)
In an alternative particularly preferred embodiment, R5 is hydroxy.
R" is preferably independently fluorine, chlorine, C1-C2alkyl. Clfluoroalkyl, C,-
C2alkoxy or Clfluoroalkoxy.
12 Preferably each R1 2 -I S -~ ndependentlyh alo, nitro, C1-C4alkyl,C i-C4haloalkyl or Cl-
C4alkoxy. Examples of such preferred groups are chloro, fluoro, nitro, methyl, ethyl,
trifluoromethyl and methoxy.
Preferably, the compound of formula (I) is one of compounds A1 and A2, which
have the structures shown in Table A provided hereinafter, or an agriculturally
acceptable salt thereof.
Processes for preparing the compound of formula (I)
The compounds of the invention may be made by a variety of methods, for
example, by the methods described in Schemes 1 to 6.
In the following schemes, compounds of formula (1) where R ~ot~heSr th an exemplified
below can be made using analogous processes known to the person skilled in the art.
Scheme 1
halogenating
agent
0:
X
0
1) Compounds of formula (F) wherein R~ is as defined for a compound of formula
(I) can be prepared by reaction of a benzyl compound of formula (E) wherein R4 is as
defined for a compound of formula (I) and X is a leaving group such as halogen, e.g.
bromine, or a mesylate, or a tosylate with a metal sulfite, such as sodium sulfite, as
shown in Scheme 1. For example, if (E) is a benzyl bromide (i.e. where X is bromine)
the reaction can conveniently be carried out in a suitable solvent, such as water,
optionally in the presence of a suitable co-solvent, such as acetone, optionally using
heating or microwave heating. Similar methods have been described, for example, in
Synthetic Communications 25(9), 1303, 1995. Compounds of formula (E) are
commercially available or can be made by methods known to the person skilled in the
art. A route to certain benzyl halides is, for example, described in Scheme 5 below.
2) Compounds of formula (G) wherein R4 is as defined for a compound of
formula (I) and X is halogen, such as chlorine, can be prepared by treating a compound
of formula (F) as defined in 1) with a halogenating agent, such as phosphorus
pentachloride, optionally in a suitable solvent, such as toluene, optionally using heating
or microwave heating.
3) Compounds of formula (G) wherein R4 is as defined for a compound of
formula (I) and X is halogen, such as chlorine, can be prepared by methods as
described in Synthesis, (24), 4131-4134; 2006
Scheme 2
+ base
0
1 R3LG, base
4) Compounds of formula (J) wherein A', A2, A3, R and R4 are as defined for a
compound of formula (I) and R' is C1-C~alkycl an be prepared by reaction of an amino
ester of formula (H) wherein A', A2 and A3 are as defined for a compound of formula (I)
and R' is H or Cl-C6alkyl with an acid derivative of formula (G) as defined in Scheme 1.
For example, if (G) is a sulfonyl chloride (i.e. where X is chlorine) the reaction can
conveniently be carried out in the presence of a base, such as triethylamine or pyridine,
in a suitable solvent, such as acetonitrile or dichloromethane, optionally using heating or
microwave heating. Compounds of formula (H) are commercially available or can be
made by methods known to the person skilled in the art.
5) Compounds of formula (K), wherein A', A2, A3, R, R3 and R~ are as defined for
a compound of formula (I) and R2 is H or Cq-C~alkycI an be prepared from a conipound
of formula (J) as defined in 4) by reaction with a compound of formula R~LGw herein R3
is as defined for a compound of formula (I) other than hydrogen, and LG is a leaving
group such as a halide, for example bromide or iodide, or tosylate, mesylate or triflate,
with a base, such as N,N-diisopropylethylamine, in a suitable solvent, such as
acetonitrile, optionally using heating or microwave heating.
6) Compounds of formula (D), i.e. a compound of formula (I) wherein A', A', A3,
R, R3 and R4 is as defined for a compound of formula (I) other than R3 is hydrogen and
R5 is hydroxy, can be prepared by treating a compound of formula (K) as defined in 5)
with a base, such as lithium hexamethyldisilazide, sodium hexamethyldisilazide or
potassium carbonate, in a suitable solvent, such as tetrahydrofuran or N, Ndimethylformamide,
optionally using heating or microwave heating.
7) Compounds of formula (L), i.e. a compound of formula (I) wherein A', A', A3,
R, R3 and R4 is as defined for a compound of formula (I) other than R3 is hydrogen and
R5 is -O-CO-R1O, can be prepared by reaction of a compound of formula (D) as defined
in 6) with an acid chloride of formula R'OCOCI or an acid anhydride of formula
(R'°C0)20 wherein R'O is as defined for a compound of formula (I), optionally in the
presence of a base, such as pyridine andlor 4-dimethylaminopyridine, optionally in a
suitable solvent, such as dichloromethane or acetonitrile, optionally using heating or
microwave heating.
Scheme 3
base
I
0=?-R4
0
H
(J) (A)
I
8) Compounds of formula (A) wherein A', A2, A3, R. R3, R4 and R" is as defined
for a compound of formula (I) and R3 is hydrogen and R5 is hydroxy, can be prepared by
treating a compound of formula (J) as defined in 4) with a base, such as lithium
hexamethyldisilazide, sodium hexamethyldisilazide or potassium carbonate, in a suitable
solvent, such as tetrahydrofuran or N,N-dimethylformamide, optionally using heating or
microwave heating, as shown in Scheme 3.
9) Compounds of formula (M), i.e. a compound of formula (I) wherein A', A', A3,
R, R3, R4 and R" is as defined for a compound of formula (I) and R3 is hydrogen and R5
is -0-CO-Rc"a, n be prepared by reaction of a compound of formula (A) as defined in
7) with an acid chloride of formula Rl0COCl or an acid anhydride of formula (R'°C0)20
wherein R'O is as defined for a compound of formula (I), optionally in the presence of a
base, such as pyridine, optionally in a suitable solvent, such as dichloromethane,
optionally using microwave heating.
Scheme 4
R3LG.
base
P A ,ssO
A, N \b I
H
(M)
base
RQLG,
-base
10) Compounds of formula (L) as defined in 7) can be prepared from a
compound of formula (M) as defined in 9) by reaction with a compound of formula R~LG
as defined in 5) in the presence of a base, such as N,N-diisopropylethylamine, in a
suitable solvent, such as acetonitrile or N, N-dimethylformamide, optionally using heating
or microwave heating, as shown in Scheme 4.
11) Compounds of formula (D) as defined in 6) can be prepared by treating a
compound of formula (L) as defined in 7) with a base, such as sodium hydroxide, in a
suitable solvent, such as aqueous tetrahydrofuran or aqueous methanol.
12) Compounds of formula (P), i.e. a compound of formula (I) wherein A', A2, A3,
R, R ~a,n d R4 are as defined for a compound of formula (I) and R3 is as defined for a
compound of formula (I) other than hydrogen and R5 is -0-R9, can be prepared from a
compound of formula (D) as defined in 6) by reaction with a compound of formula R9LG
wherein R9 is as defined for a compound of formula (I) and LG is a leaving group such
as halide, for example bromide or iodide, or tosylate, mesylate or triflate, in the presence
of a base, such as potassium carbonate, in a suitable solvent, such as N, Ndimethylformamide
or acetonitrile.
Scheme 5
13) In certain cases where benzyl halides are not commercially available it is
necessary to make them. A typical synthesis is shown in Scheme 5. Benzyl halides of
formula (T) wherein R~ is as defined for a compound of formula (I) and X is halogen,
such as bromine, can be made from a substituted toluene of formula (S) wherein R~ is
as defined for a compound of formula (I), with a halogenating agent, such as halogen of
formula X2 wherein X is chlorine or bromine, in the presence of light, or a Nhalosuccinimide
of formula
wherein X is chlorine, bromine or iodine, in the presence of a radical initiator, such as
benzoyl peroxide, in a suitable solvent, such as carbon tetrachloride, and optionally in
the presence of a light source, such as a 500 watt tungsten halogen lamp, at reflux.
Scheme 6
14) Compounds of formula (2) wherein R3 and R4 are as defined for a compound
of formula (I) can be prepared by reaction of an amine of formula (1) wherein R3 is as
defined for a compound of formula (I) with an acid derivative of formula (G) as defined in
2) as shown in Scheme 6. For example, if (G) is a sulfonyl chloride (i.e. where X is
chlorine) the reaction can conveniently be carried out in the presence of a base, such as
triethylamine or pyridine, in a suitable solvent, such as acetonitrile or dichloromethane,
optionally using heating or microwave heating. Amines of formula (1) are commercially
available or can be made by methods known to the person skilled in the art.
15) Compounds of formula (D) as defined in 6) can be prepared by reaction of a
sulfonamide derivative of formula (2) as defined in 14) with a compound of formula (3)
wherein R2 is as defined in 4) and X is as defined in 1). The reaction can conveniently
be carried out in the presence of a base, such as potassium carbonate or lithium bis
(trimethylsilamide), in a suitable solvent, such as N,N-dimethylformamide, optionally
using heating or microwave heating. Alternatively the reaction can be carried out using
metal cross coupling conditions such as those described in Org. Lett. 2004, 6, 14, 2433.
Under both reaction conditions, and particularly when R2 is H, compounds of formula (K)
as defined in 5) can be produced. Compounds of formula (K) where R2 is H can be
converted to compounds of formula (D) by methods known to the person skilled in the
art. Compounds of formula (K) where R2 is not H may be obtained from compounds of
formula (K) where R2 is hydrogen by standard esterification methods and then to
compounds of formula (D) by methods known to the person skilled in the art.
Compounds of formula (3) are commercially available or can be made by methods
known to the person skilled in the art.
Herbicidal compositions, methods of use, and mixtures
The compounds of formula (I) according to the invention can be used as
herbicides in unmodified form, as obtained in the synthesis, but they are generally
formulated into herbicidal compositions in various ways my mixing with various
substances (e.g. inert (i.e. substantially non-herbicidal) substances), such as carriers,
solvents, adjuvants andlor surface-active substances.
The present invention therefore also provides a herbicidal composition (e.g.
liquid herbicidal composition) which comprises a compound of formula (I) (e.g. a
herbicidally effective amount thereof), and preferably also a carrier (e.g. liquid or solid
carrier) andlor one or more solvents; and optionally also an adjuvant andlor a surfaceactive
substance.
The herbicidal compositions (e.g. formulations) of the invention disclosed can be
in various physical forms, for example in the form of dusting powders, gels, wettable
powders, water-dispersible granules, water-dispersible tablets, effervescent pellets,
emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oilflowables,
aqueous dispersions, oily dispersions, suspo-emulsions, capsule
suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with
water or a water-miscible organic solvent as carrier), impregnated polymer films or in
other forms known e.g, from the Manual on Development and Use of FA0 Specifications
for Plant Protection Products, 5th Edition, 1999. The herbicidal compositions (e.g.
formulations) can either be used directly or they are diluted prior to use. The dilutions
can be made, for example, with water, liquid fertilisers, micronutrients, biological
organisms, oil or solvents.
The herbicidal compositions (e.g. formulations) can be prepared for example, by
mixing the active ingredient with the formulation adjuvants in order to obtain
compositions in the form of finely divided solids, granules, solutions, dispersions or
emulsions. The active ingredients can also be formulated with other adjuvants, such as
finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of
vegetable or animal origin, organic solvents, water, surface-active substances or
combinations thereof. The active ingredients can also be contained in very fine microcapsules
consisting of a polymer. Microcapsules contain the active ingredients in a
porous carrier. This enables the active ingredients to be released into the environment in
controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from
0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to
95% by weight of the capsule weight. The active ingredients can be in the form of a
monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of
a suitable solution. The encapsulating membranes comprise, for example, natural or
synthetic rubbers, cellulose, styrenelbutadiene copolymers, polyacrylonitrile,
polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified
polymers and starch xanthates or other polymers that are known to the person skilled in
the art in this connection.
Alternatively, very fine microcapsules can be formed in which the active
ingredient is contained in the form of finely divided particles in a solid matrix of base
substance, but the microcapsules are not themselves encapsulated.
The inert substances that are suitable for the preparation of the compositions
according to the invention are known per se.
As liquid carriers there may be used: water, toluene, xylene, petroleum ether,
vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides,
acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate,
chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone
alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol,
diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether,
diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, I ,4-dioxane,
dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate,
diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate,
1 , I ,I-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene
glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone,
glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene
glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene,
isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl
isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate,
methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine
acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400),
propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol
methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic
acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl
acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether,
methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl
alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol,
glycerol, N-methyl-2-pyrrolidone and the like. Water is generally the liquid carrier of
choice for diluting the concentrates.
Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay,
silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium
montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour,
ground walnut shells, lignin and similar substances, as described, for example, in CFR
180.1001. (c) & (d).
A large number of surface-active substances can advantageously be used in
both solid and liquid formulations, especially in those formulations which can be diluted
with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic
or polymeric and they can be used as emulsifiers, wetting agents or suspending agents
or for other purposes. Typical surface-active substances include, for example, salts of
alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates,
such as calcium dodecylbenzenesulfonate; alkylphenollalkylene oxide addition products,
such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as
tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of
alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters
of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters,
such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride,
polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block
copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkylphosphate
esters; and also further substances described e.g. in "McCutcheon's
Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey,
1981.
Further inert substances that can typically be used in herbicidal compositions
(e.g. formulations) include crystallisation inhibitors, viscosity modifiers, suspending
agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries,
antifoams, complexing agents, neutralizing or pH-modifying substances and buffers,
corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients,
plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and
also liquid and solid fertilizers.
The compositions according to the invention can additionally include an additive
comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or
mixtures of such oils and oil derivatives. The amount of oil additive in the composition
according to the invention is generally from 0.01 to lo%, based on the spray mixture.
For example, the oil additive can be added to the spray tank in the desired concentration
after the spray mixture has been prepared. Preferred oil additives comprise mineral oils
or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil,
emulsified vegetable oil, such as AMIGO@ (RhBne-Poulenc Canada Inc.), alkyl esters of
oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin,
such as fish oil or beef tallow. A preferred additive contains, for example, as active
components essentially 80% by weight alkyl esters of fish oils and 15% by weight
methylated rapeseed oil, and also 5% by weight of customary emulsifiers and pH
modifiers. Especially preferred oil additives comprise alkyl esters of c 8 - C ~fa tty acids,
especially the methyl derivatives of C,,-C,* fatty acids, for example the methyl esters of
lauric acid, palmitic acid and oleic acid, being of importance. Those esters are known as
methyl laurate (CAS-111-82-O), methyl palmitate (CAS-112-39-0) and methyl oleate
(CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery@ 2230 and
2231 (Cognis GmbH). Those and other oil derivatives are also known from the
Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.
The application and action of the oil additives can be further improved by
combination with surface-active substances, such as non-ionic, anionic or cationic
surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed
on pages 7 and 8 of WO 97134485. Preferred surface-active substances are anionic
surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and
also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is
given to ethoxylated C,2-C22 fatty alcohols having a degree of ethoxylation of from 5 to
40. Examples of commercially available surfactants are the Genapol types (Clariant
AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified
heptamethyltriloxanes which are commercially available e.g. as Silwet L-770, and also
perfluorinated surfactants. The concentration of the surface-active substances in relation
to the total additive is generally from 1 to 30% by weight. Examples of oil additives
consisting of mixtures of oil or mineral oils or derivatives thereof with surfactants are
Edenor ME SUO, Turbocharge@ (Syngenta AG, CH) or ActipronC (BP Oil UK Limited,
GB).
If desired, it is also possible for the mentioned surface-active substances to be
used in the formulations on their own, that is to say without oil additives.
Furthermore, the addition of an organic solvent to the oil additivelsurfactant
mixture may contribute to an additional enhancement of action. Suitable solvents are, for
example, SolvessoO (ESSO) or Aromatic Solvent@ (Exxon Corporation). The
concentration of such solvents can be from 10 to 80% by weight of the total weight. Oil
additives that are present in admixture with solvents are described, for example, in USA-
4,834,908. A commercially available oil additive disclosed therein is known by the
name MERGE@ (BASF Corporation). A further oil additive that is preferred according to
the invention is SCORE@ (Syngenta Crop Protection Canada).
In addition to the oil additives listed above, for the purpose of enhancing the
action of the compositions according to the invention it is also possible for formulations
of alkylpyrrolidones (e.g. AgrimaxO) to be added to the spray mixture. Formulations of
synthetic lattices, e.g. polyacrylamide, polyvinyl compounds or poly-I-p-menthene (e.g.
Bond@, CourierO or EmeraIda) may also be used. It is also possible for solutions that
contain propionic acid, for example Eurogkem Pen-e-trateO, to be added to the spray
mixture as action-enhancing agent.
The herbicidal compositions generally comprise from 0.1 to 99% by weight,
especially from 0.1 to 95% by weight, compounds of formula (I) and from 1 to 99.9% by
weight of a formulation adjuvant which preferably includes from 0 to 25% by weight of a
surface-active substance. Whereas commercial products will preferably be formulated
as concentrates, the end user will normally employ dilute formulations.
Preferred formulations have especially the following compositions (% = percent
by weight):
Emulsifiable concentrates:
active ingredient: 1 to 95%, preferably 60 to 90%
surface-active agent: 1 to 30%, preferably 5 to 20%
liquid carrier: 1 to 80%, preferably 1 to 35%
Dusts:
active ingredient: 0.1 to lo%, preferably 0.1 to 5%
solid carrier: 99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates:
active ingredient: 5 to 75%, preferably 10 to 50%
water: 94 to 24%, preferably 88 to 30%
surface-active agent: 1 to 40%, preferably 2 to 30%
Wettable powders:
active ingredient: 0.5 to 90%, preferably 1 to 80%
surface-active agent: 0.5 to 20%, preferably 1 to 15%
solid carrier: 5 to 95%, preferably 15 to 90%
Granules:
active ingredient: 0.1 to 30%, preferably 0.1 to IS%
solid carrier: 99.5 to 70%, preferably 97 to 85%
The following formulation examples further illustrate, but do not limit, the invention
Formulation examples for herbicides of formula (I) (% = percent by weiqht)
F1. Emulsifiable concentrates a) b) C) d)
active ingredient 5% 10% 25% 50%
calcium dodecylbenzenesulfonate 6% 8% 6% 8%
castor oil polyglycol ether 4% . 4% 4%
(36 mol of ethylene oxide)
octylphenol polyglycol ether 4% 2%
(7-8 mol of ethylene oxide)
NMP - 10% 20%
arom. hydrocarbon mixture 85% 78% 55% 16%
C9-cl2
Emulsions of any desired concentration can be obtained from such concentrates by
dilution with water.
F2. Solutions
active ingredient
1 -methoxy-3-(3-methoxypropoxy)-
propane 20% 20% .
polyethylene glycol MW 400 20% 10%
NMP 30% 10%
arom. hydrocarbon mixture 75% 60% -
c9-c12
The solutions are suitable for use in the form of microdrops.
F3. Wettable powders a) b) C) d)
active ingredient 5% 25% 50% 80%
sodium lignosulfonate 4% 3%
sodium lauryl sulfate 2% 3% - 4%
sodium diisobutylnaphthalenesulfonate
- 6% 5% 6%
octylphenol polyglycol ether 1 % 2%
(7-8 mol of ethylene oxide)
highly dispersed silicic acid 1% 3% 5% 10%
kaolin 88% 62% 35%
The active ingredient is mixed thoroughly with the adjuvants and the mixture is
thoroughly ground in a suitable mill, affording wettable powders which can be diluted
with water to give suspensions of any desired concentration.
F4. Coated qranules a) b) C)
active ingredient 0.1% 5% 15%
highly dispersed silicic acid 0.9% 2% 2%
[inorganic carrier 99.0% 93% 83%
(diameter 0.1 - 1 mm)
for example CaC03 or SiO*]
The active ingredient is dissolved in methylene chloride and applied to the carrier by
spraying, and the solvent is then evaporated off in vacuo.
F5. Coated qranules a) b) C)
active ingredient 0.1% 5% 15%
polyethylene glycol MW 200 1 .O% 2% 3%
highly dispersed silicic acid 0.9% 1 % 2%
[inorganic carrier 98.0% 92% 80%
(diameter 0.1 - Imm)
for example CaC03 or Si02]
The finely ground active ingredient is uniformly applied, in a mixer, to the carrier
moistened with polyethylene glycol. Non-dusty coated granules are obtained in this
manner.
F6. Extruder qranules a) b) C) d)
active ingredient 0.1% 3% 5% 15%
sodium lignosulfonate 1.5% 2% 3% 4%
carboxymethylcellulose 1.4% 2% 2% 2%
kaolin 97.0% 93% 90% 79%
The active ingredient is mixed and ground with the adjuvants, and the mixture is
moistened with water. The mixture is extruded and then dried in a stream of air.
~ 7D.US ~S a) b) c)
active ingredient 0.1% 1 % 5%
talcum 39.9% 49% 35%
kaolin 60.0% 50% 60%
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and
grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) C) d)
act/ve ingredient 3% 10% 25% 50%
ethylene glycol 5% 5% 5% 5%
nonylphenol polyglycol ether 1 % 2%
(1 5 mol of ethylene oxide)
sodium lignosulfonate 3% 3% 4% 5%
carboxymethylcellulose 1 % 1% 1% 1%
37% aqueous formaldehyde 0.2% 0.2% 0.2% 0.2%
solution
silicone oil emulsion 0.8% 0.8% 0.8% 0.8%
water 87% 79% 62% 38%
The finely ground active ingredient is intimately mixed with the adjuvants, giving a
suspension concentrate from which suspensions of any desired concentration can be
obtained by dilution with water
Methods of use
The present invention further relates to a method of controlling a plant (e.g. a
grass andlor a weed) which comprises applying to the plant (e.g. to a crop of useful
plants) or to the locus thereof a herbicidally effective amount of a compound of formula
(1).
The invention also relates to a method of inhibiting plant growth (e.g. in a grass
andlor a weed) which comprises applying to the plant (e.g. to a crop of useful plants) or
to the locus thereof a herbicidally effective amount of a compound of formula (I).
The invention also relates to a method of selectively controlling a grass andlor a
weed in a crop of useful plants which comprises applying to the useful plants or locus
thereof or to the area of cultivation a herbicidally effective amount of a compound of
formula (I).
A compound of formula (I), andlor a herbicidal composition andlor mixture
containing the same, may also be applied to turf, pasture, rangeland, a right of way etc.
In particular they may be used on a golf-course, a lawn, a park, a sports-field, a racecourse
or similar.
The term "herbicide" as used herein means a compound that controls or modifies
the growth of plants. The term "herbicidally effective amount" means the quantity of such
a compound or combination of such compounds that is capable of producing a
controlling or modifying effect on the growth of plants. Controlling or modifying effects
include all deviation from natural development, for example: killing, retardation, leaf
burn, albinism, dwarfing or similar. The term "plant" or "plants" refers to all physical
parts of a plant, such as seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage,
or fruits. The term "locus" is intended to include soil, seeds, or seedlings, as well as
established vegetation.
The crop of useful plants, e.g. in or to which a compound, composition, mixture
or method according to the invention can be used or applied, can for example be a
perennial crop, such as citrus fruit, grapevines, nuts, oil palms, olives, pome fruit, stone
fruit or rubber; or an annual arable crop, such as a cereal (e.g. wheat, barley, rye, or
triticale, etc.), cotton, oilseed rape, maize (corn), rice, soybean, sugarbeet, sugarcane,
sunflowers, an ornamental or a vegetable; especially a cereal, maize or soybean.
The grass andlor weed to be controlled can be monocotyledonous andlor
dicotyledonous species. The grass andlor weed to be controlled can be a
monocotyledonous species, for example Agrostis, Alopecurus (e.g. Alopecurus
myosuroides), Avena (e.g. Avena fatua), Bromus, Cyperus, Digitaria (e.g. Digitaria
sanguinalis), Echinochloa (e.g. Echinochloa crus-galli), Lolium (e.g. Lolium perenne).
Monochoria, Rottboellia, Sagittaria, Scirpus. Setaria (e.g. Setaria faberi), or Sorghum; or
more preferably is a dicotyledonous species, for example Abutilon (e.g. Abutilon
theophrasti), Amaranthus (e.g. Amaranthus retroflexus), Bidens (e.g. Bidens pilosa),
Chenopodium (e.g. Chenopodium album), Chrysanthemum. Euphorbia (e.g. Euphorbia
hetrophylla), Galium (e.g. Galium aparine), lpomoea (e.g. lpomea hederaceae),
Nasturtium, Sida (e.g. Sida spinosa), Sinapis (e.g. Sinapis arvensis), Solanum (e.g.
Solanum nigrum), Stellaria (e.g. Stellaria media), Veronica (e.g. Veronica persica or
Veronica hederifolia), Viola (e.g. Viola arvensis) or Xanthium.
Crops are to be understood as also including those crops which have been
rendered tolerant to herbicides or classes of herbicides (e.g. auxins or ALS-, GS-,
EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic
engineering. An example of a crop that has been rendered tolerant to imidazolinones,
e.g. imazamox, by conventional methods of breeding is Clearfield@ summer rape
(canola). Examples of crops that have been rendered tolerant to herbicides by genetic
engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties
commercially available under the trade names RoundupReadyB and LibertyL~nke.
Crops are also to be understood as including those which have been rendered
resistant to harmful insects by genetic engineering methods, for example Bt maize
(resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt
potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize
hybrids of NK@ (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by
Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to
synthesize such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93107278,
WO 95134656, WO 031052073 and EP-A-427 529. Examples of transgenic plants
comprising one or more genes that code for an insecticidal resistance and express one
or more toxins are KnockOutB (maize), Yield GardB (maize), NuCOTIN33BB (cotton),
BollgardB (cotton), NewLeam (potatoes), NatureGardB and ProtexctaB. Plant crops or
seed material thereof can be both resistant to herbicides and, at the same time, resistant
to insect feeding ("stacked" transgenic events). For example, seed can have the ability
to express an insecticidal Cry3 protein while at the same time being tolerant to
glyphosate.
Crops are also to be understood as including those which are obtained by
conventional methods of breeding or genetic engineering and contain so-called output
traits (e.g. improved storage stability, improved stress (e.g. drought) resistance, higher
nutritional value andlor improved flavor).
Areas under cultivation include land on which the crop plants are already
growing and land intended for cultivation with those crop plants. The compounds of the
invention can be applied before weeds emerge (pre-emergence application) or after
weeds emerge (post-emergence application), and are particularly effective when applied
post-emergence.
The rates of application of compounds of formula (I) (e.g. rate of application to a
crop of useful plants, or to a grass andlor a weed, or to the locus thereof, or to the area
of cultivation) may vary within wide limits and may depend on the nature of the soil, the
method of application (pre- or post-emergence; seed dressing; application to the seed
furrow; no tillage application etc., whether the compound of formula (I) is applied as a
mixture with a further herbicide), the crop plant, the grass andlor weed to be controlled,
the prevailing climatic conditions, andlor other factors governed by the method of
application, the time of application and the target crop. The compounds of formula (I)
according to the invention, are generally applied (e.g. to a crop of useful plants, or to a
grass andlor a weed, or to the locus thereof, or to the area of cultivation) at a rate of
from 10 to 2000 glha, in particular from 50 to 1000 glha, e.g, whether applied as a sole
herbicide or as a mixture containing a further herbicide.
Mixtures I combinations
The compounds of formula (I) according to the invention can also be used in
combination with one or more further herbicides. Some of the combinations 1 mixtures
may lead to synergistic effects andlor may confer one or more technical effects andlor
advantages. For this reason, preferred mixtures are those containing a compound of
formula (I) and a HPPD inhibitor.
The invention therefore provides a mixture (e.g. herbicidal composition, e.g.
liquid or solid), which comprises a herbicidally effective amount of a compound of
formula (I), and a further herbicide as a mixture partner for the compound of formula (I).
In particular, the following mixtures of the compound of formula (I) are important,
where numbers given in brackets after compound names are often the corresponding
reference numbers given in The Pesticide Manual, 13th Edition (BCPC), 2003:
Mixtures of a compound of formula (I) with a synthetic auxin (e.g. a compound of
formula (I) with clopyralid (162); a compound of formula (I) with 2,4-D (21 1); a
compound of formula (I) with dicamba (228); a compound of formula (I) with diphenamid
(274); a compound of formula (I) with MCPA (499); a compound of formula (I) with
quinclorac (712); a compound of formula (I) with aminopyralid (CAS RN 1501 14-71-9); a
compound of formula (I) with 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxypheny1)-2-
pyridinecarboxylic acid (CAS RN 943832-60-8); or a compound of formula (I) with
4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid,
methyl ester (CAS RN 943831-98-9)).
Mixtures of a compound of formula (I) with diflufenzopyr (252).
Mixtures of a compound of formula (I) with an acetanilide (e.g. a compound of
formula (I) with acetochlor (5), a compound of formula (I) with dimethenamid (260), a
compound of formula (I) with metolachlor (548), a compound of formula (I) with Smetolachlor
(549), or a compound of formula (I) with pretilachlor (656)).
Mixtures of a compound of formula (I) with flamprop-M (355).
Mixtures of a compound of formula (I) with flufenacet (BAY FOE 5043) (369).
Mixtures of a compound of formula (I) with pyroxasulfone (CAS RN 447399-55-
5).
Mixtures of a compound of formula (I) with an HPPD inhibitor (e.g. a compound
of formula (I) with pyrazolynate CAS 5801 1-68-0 (sometimes called pyrazolate), a
compound of formula (I) with benzofenap, a compound of formula (I) with isoxachlortole,
a compound of formula (I) with tefuryltrione, a compound of formula (I) with pyrazoxyfen,
a compound of formula (I) with benzobicyclon, a compound of formula (I) with
isoxaflutole (479), a compound of formula (I) with mesotrione (515), a compound of
formula (1) with pyrasulfotole (CAS RN 365400-1 1-9), a compound of formula (I) with
sulcotrione (747), a compound of formula (I) with tembotrione (CAS RN 335104-84-2),
compound of formula (I) with topramezone (CAS RN 210631-68-8), a compound of
formula (I) with bicyclopyrone (CAS RN 352010-68-5), or compound of formula (I) with
4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-
bicyclo[3.2.l]oct-3-en-2-one (CAS RN 894355-80-7)).
Mixtures of a compound of formula (I) with a triazine (e.g. a compound of formula
(I) with atrazine (37); or a compound of formula (I) with terbuthylazine (775)).
Mixtures of a compound of formula (I) with a triazine and an HPPD inhibitor (e.g.
a compound of formula (I) with triazine and pyrazolynate, a compound of formula (I) with
triazine and benzofenap, a compound of formula (I) with triazine and isoxachlortole, a
compound of formula (I) with triazine and tefuryltrione, a compound of formula (I) with
triazine and pyrazoxyfen, a compound of formula (I) with triazine and benzobicyclon, a
compound of formula (I) with triazine and isoxaflutole, a compound of formula (I) with
triazine and mesotrione, a compound of formula (I) with triazine and pyrasulfotole, a
compound of formula (I) with triazine and sulcotrione, a compound of formula (I) with
triazine and tembotrione, a compound of formula (I) with triazine and topramezone,
compound of formula (I) with triazine and bicyclopyrone, or a compound of formula (I)
with triazine and 4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-
pyridinyl]carbonyl]-bicyclo[3.2.l]oct-3-en-2-one).
Mixtures of a compound of formula (I) with glyphosate (419).
Mixtures of a compound of formula (I) with glyphosate and an HPPD inhibitor
(e.g. a compound of formula (I) with glyphosate and pyrazolynate, a compound of
formula (I) with glyphosate and benzofenap, a compound of formula (I) with glyphosate
and isoxachlortole, a compound of formula (I) with glyphosate and tefuryltrione, a
compound of formula (1) with glyphosate and pyrazoxyfen, a compound of formula (I)
with glyphosate and benzobicyclon, a compound of formula (I) with glyphosate and
isoxaflutole, a compound of formula (I) with glyphosate and mesotrione, a compound of
formula (I) with glyphosate and pyrasulfotole, a compound of formula (I) with glyphosate
and sulcotrione, a compound of formula (I) with glyphosate and tembotrione, a
compound of formula (I) with glyphosate and topramezone, a compound of formula (I)
with glyphosate a compound of formula (I) with glyphosate and bicyclopyrone, or a
compound of formula (I) with glyphosate and 4-hydroxy-3-[[2-(3-methoxypropy1)-6-
(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.l]oct-3-en-2-one).
Mixtures of a compound of formula (I) with glufosinate-ammonium (418).
Mixtures of a compound of formula (I) with glufosinate-ammonium and an HPPD
inhibitor (e.g. a compound of formula (I) with glufosinate-ammonium and pyrazolynate, a
compound of formula (I) with glufosinate-ammonium and benzofenap, a compound of
formula (I) with glufosinate-ammonium and isoxachlortole, a compound of formula (I)
with glufosinate-ammonium and tefuryltrione, a compound of formula (I) with glufosinateammonium
and pyrazoxyfen, a compound of formula (I) with glufosinate-ammonium and
benzobicyclon, a compound of formula (I) with glufosinate-ammonium and isoxaflutole, a
compound of formula (I) with glufosinate-ammonium and mesotrione, a compound of
formula (I) with glufosinate-ammonium and pyrasulfotole, a compound of formula (I) with
glufosinate-ammonium and sulcotrione, a compound of formula (I) with glufosinateammonium
and tembotrione, a compound of formula (I) with glufosinate-ammonium and
topramezone, a compound of formula (I) with glufosinate-ammonium and bicyclopyrone,
or a compound of formula (I) with glufosinate-ammonium with 4-hydroxy-3-[[2-(3-
methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyc10[3.2.1]oct-3-en-2-one).
Mixtures of a compound of formula (I) with an ALS or an AHAS inhibitor (e.g. a
compound of formula (I) with bensulfuron-methyl (64), a compound of formula (I) with
chlorimuron-ethyl (135), compound of formula (I) with cloransulam-methyl (164), a
compound of formula (I) with florasulam (359), a compound of formula (I) with
flucarbazone-sodium (364), a compound of formula (I) with imazamox (451), a
compound of formula (I) with imazapyr (453), a compound of formula (I) with
imazethapyr (455), a compound of formula (I) with iodosulfuron-methyl-sodium (466), a
compound of formula (I) with mesosulfuron-methyl (514), a compound of formula (I) with
nicosulfuron (577), a compound of formula (I) with penoxsulam (622), a compound of
formula (I) with pyroxsulam (triflosulam) (CAS RN 422556-08-9), a compound of formula
(I) with thifensulfuron-methyl (thiameturon-methyl) (795), a compound of formula (I) with
triasulfuron (817), a compound of formula (I) with tribenuron-methyl (822), a compound
of formula (I) with trifloxysulfuron-sodium (833), a compound of formula (I) with
thiencarbazone (4-[(4,5-dihydro-3-methoxy-4-methyl-5-0x0-I H-I ,2,4-triazol-Iyl)
carbonylsulfamoyl]-5-methylthiophene-3-carboxylic acid, BAY636)), or a compound of
formula (I) with thiencarbazone-methyl (methyl 4-[(4,5-dihydro-3-methoxy-4-methyl-5-
0x0-1 H-1,2,4-triazol-1-yl)carbonylsulfamoyI]-5-methylthiophene-3-carboxylate, CAS RN
317815-83-1, BAY636-methyl)).
Mixtures of a compound of formula (I) with a PPO inhibitor (e.g. compound of
formula (I) with acifluorfen-sodium (7), a compound of formula (I) with butafenacil (IOI),
a compound of formula (I) with carfentrazone-ethyl (121), a compound of formula (I) with
cinidon-ethyl (152), a compound of formula (I) with flumioxazin (376), a compound of
formula (I) with fomesafen (401), a compound of formula (I) with lactofen (486), or a
compound of formula (I) with [3-[2-chloro-4-fluoro-5-(l-methyl-6-trifluoromethyl-2,4-
dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester)
(CAS RN 353292-31-6)).
Mixtures of a compound of formula (I) with an acetyl-CoA carboxylase inhibitor
(ACCase inhibitor) (e.g. a compound of formula (I) with butroxydim (106), a compound
of formula (I) with clethodim (155), a compound of formula (I) with clodinafop-propargyl
(1 56), a compound of formula (I) with cycloxydim (1 go), a compound of formula (I) with
cyhalofop-butyl (195), a compound of formula (I) with diclofop-methyl (238), a compound
of formula (I) with fenoxaprop-P-ethyl (339), a compound of formula (I) with fluazifopbutyl
(361), a compound of formula (I) with fluazifop-P-butyl (362), a compound of
formula (I) with haloxyfop (427), a compound of formula (I) with haloxyfop-P (428), a
compound of formula (I) with propaquizafop (670), a compound of formula (I) with
quizalofop (717), a compound of formula (I) with quizalofop-P (718), compound of
formula (I) with sethoxydim (726), a compound of formula (I) with tepraloxydim (771), a
compound of formula (I) with tralkoxydim (81 I)), or a compound of formula (I) with
pinoxaden (CAS RN 243973-20-8).
Mixtures of a compound of formula (I) with prosulfocarb (683), or a compound of
formula (I) with tri-allate (816).
Mixtures of a compound of formula (I) with bromoxynil (95), a compound of
formula (I) with chloridazon (134), a compound of formula (I) with chlorotoluron (143), a
compound of formula (I) with diuron (281), or a compound of formula (I) with metribuzin
(554).
Mixtures of a compound of formula (I) with clomazone (159), a compound of
formula (I) with diflufenican (251), a compound of formula (I) with flurochloridone (389),
or a compound of formula (I) with flurtamone (392).
Mixtures of a compound of formula (I) with pendimethalin (621) or a compound of
formula (I) with trifluralin (836).
Mixtures of a compound of formula (I) with difenzoquat rnetilsulfate (248).
Mixtures of a compound of formula (I) with diquat dibromide (276).
Mixtures of a compound of formula (I) with paraquat dichloride (614).
The mixing partners of the compound of formula (I) may also be in the form of
esters or salts, as mentioned for example in The Pesticide Manual, 13th Edition (BCPC),
2003. The reference to glufosinate-ammonium also applies to glufosinate, the reference
to cloransulam-methyl also applies to cloransulam, the reference to dimethenamid also
applies to dimethenamid-P, the reference to flamprop-M also applies to flamprop, and
the reference to pyrithiobac-sodium also applies to pyrithiobac, etc.
The mixing ratio of the compound of formula (I) to the mixing partner (e.g, further
herbicide) is typically from 1: 300 to 300:l by weight or from 1: 100 to 100:l by weight;
or preferably from 1: 30 to 30:l by weight.
The mixtures can advantageously be used in the above-mentioned formulations
(in which case "active ingredient" relates to the respective mixture of compound of
formula (I) with the mixing partner).
Additionally, one or more of the following further herbicides or plant growth
regulators (typically plant growth inhibitors) can be used in combination with a
compound of formula (I) according to the invention or in combination with a mixture as
described above: aclonifen (8), acrolein (lo), alachlor (14), alloxydim (18), ametryn (20),
amicarbazone (21), amidosulfuron (22), aminocyclopyrachlor (CAS RN 858956-08-8),
amitrole (aminotriazole) (25), ammonium sulfamate (26), anilofos (31), asulam (36),
aviglycine (39), azafenidin (CAS RN 68049-83-2), azimsulfuron (43), BAS 800H (CAS
RN 372137-35-4), beflubutamid (53, benazolin (57), bencarbazone (CAS RN 173980-
17-I), benfluralin (59), benfuresate (61), bensulide (65), bentazone (67), benzfendizone
(CAS RN 158755-95-4) benzobicyclon (69), benzofenap (70), bilanafos (bialaphos)
(77), bispyribac-sodium (82), borax (86), bromacil (go), bromobutide (93), bromofenoxim
(CAS RN 13181-17-4), butachlor (loo), butamifos (102), butralin (105), butylate (108),
cafenstrole ( I lo), carbetamide (1 17), chlorbromuron (CAS RN 13360-45-7),
chlorflurenol-methyl (133), chloroacetic acid (138), chlorpropham (144), chlorsulfuron
(147), chlorthal-dimethyl (148), cinmethylin (153), cinosulfuron (154), clomeprop (160),
cumyluron (180), cyanamide (182), cyanazine (183), cyclanilide (186), cycloate (187),
cyclosulfamuron (189), daimuron (213), dalapon (214), dazomet (216) desmedipham
(225), desmetryn (CAS RN 1014-69-3), dichlobenil(229), dichlorprop (234), dichlorprop-
P (235), diclosulam (241), dimefuron (256), dimepiperate (257), dimethachlor (258),
dimethametryn (259), dimethipin (261), dimethylarsinic acid (264), dinitramine (268),
dinoterb (272), dipropettyn (CAS RN 4147-51-7), dithiopyr (280), DNOC (282), DSMA
(CAS RN 144-21-8), endothal(295), EPTC (299), esprocarb (303), ethalfluralin (305),
ethametsulfuron-methyl (306), ethephon (307), ethofumesate (31 I), ethoxyfen (CAS RN
188634-90-4), ethoxyfen-ethyl (CAS RN 131086-42-5), ethoxysulfuron (314),
etobenzanid (318), fentrazamide (348), ferrous sulfate (353), flazasulfuron (356),
fluazolate (isopropazol) (CAS RN 174514-07-9), flucetosulfuron (CAS RN 412928-75-7),
fluchloralin (365), flufenpyr-ethyl (371), flumetralin (373), flumetsulam (374), flumicloracpentyl
(379, flumipropyn (flumipropin) (CAS RN 84478-52-4), fluometuron (378),
fluoroglycofen-ethyl (380), flupoxam (CAS RN 119126-1 5-7), flupropacil (CAS RN
120890-70-2), flupropanate (383), flupyrsulfuron-methyl-sodium (384), flurenol (387),
fluridone (388), fluroxypyr (390), fluthiacet-methyl (395), foramsulfuron (402), fosamine
(406), halosulfuron-methyl (426), HC-252 (429), hexazinone (440), imazamethabenzmethyl
(450), imazapic (452), imazaquin (454), imazosulfuron (456), indanofan (462),
ioxynil (467), isoproturon (475), isouron (476), isoxaben (477), isoxachlortole (CAS RN
141 112-06-3), isoxapyrifop (CAS RN 87757-1 8-4), karbutilate (482), lenacil (487),
linuron (489), MCPA-thioethyl (500), MCPB (501), mecoprop (503), mecoprop-P (504),
mefenacet (505) mefluidide (507), metam (519), metamifop (mefluoxafop) (520),
metamitron (521), metazachlor (524), methabenzthiazuron (526), methazole (CAS RN
20354-26-I), methylarsonic acid (536), 1-methylcyclopropene (538), methyldymron
(539), methyl isothiocyanate (543), metobenzuron (547), metobromuron (CAS RN 3060-
89-7), metosulam (552), metoxuron (553), metsulfuron-methyl (555), MK-616 (559),
molinate (560), monolinuron (562), MSMA (CAS RN 2163-80-6), naproanilide (571),
napropamide (572), naptalam (573), neburon (574), nipyraclofen (CAS RN 99662-1 1-O),
n-methyl-glyphosate, nonanoic acid (583), notflurazon (584), oleic acid (fatty acids)
(593), orbencarb (595), orthosulfamuron (CAS RN 213464-77-8), oryzalin (597),
oxadiargyl (599), oxadiazon (600), oxasulfuron (603), oxaziclomefone (604), oxyfluorfen
(610), pebulate (617), pentachlorophenol (623), pentanochlor (624), pentoxazone (625),
pethoxamid (627), petrolium oils (628), phenmedipham (629), picloram (645),
picolinafen (646), piperophos (650), primisulfuron-methyl (657), prodiamine (661),
profluazol (CAS RN 190314-43-3), profoxydim (663), prohexadione calcium (664),
prometon (665), prometryn (666), propachlor (667), propanil (669), propazine (672),
propham (674), propisochlor (667), propoxycarbazone-sodium (procarbazone-sodium)
(679), propyzamide (681), prosulfuron (684), pyraclonil (pyrazogyl) (CAS RN 158353-
15-2), pyraflufen-ethyl (691), pyrazolynate (692), pyrazosulfuron-ethyl (694),
pyrazoxyfen (695), pyribenzoxim (697), pyributicarb (698), pyridafol (CAS RN 40020-01-
7), pyridate (702), pyriftalid (704), pyriminobac-methyl (707), pyrimisulfan (CAS RN
221205-90-9), pyrithiobac-sodium (709), quinmerac (71 3), quinoclamine (714),
rimsulfuron (721), sequestrene, siduron (727), simazine (730), simetryn (732), sodium
chlorate (734), sulfentrazone (749), sulfometuron-methyl (751), sulfosate (CAS RN
81591-81-3), sulfosulfuron (752), sulfuric acid (755), tar oils (758), TCA-sodium (760),
tebutam (CAS RN 35256-85-O), tebuthiuron (765), tefuryltrione (CAS RN 473278-76-I),
terbacil (772), terbumeton (774), terbutryn (776), thenylchlor (789), thidiazimin (CAS RN
123249-43-4), thiazafluron (CAS RN 25366-23-8), thiazopyr (793), thiobencarb (797),
tiocarbazil (807), triaziflam (819), triclopyr (827), trietazine (831), triflusulfuron-methyl
(837), trihydroxytriazine (CAS RN 108-80-5), trinexapac-ethyl (CAS RN 95266-40-3),
tritosulfuron (843), N-[(lR,2S)-2,6-dimethyl-2,3-dihydro-I Kinden-I-yl]-6-(I-fluoroethy1)-
1,3,5-triazine-2,4-diamine (CAS RN 950782-86-2), 1-(2-chloro-6-propylimidazo[1,2-
b]pyridazin-3-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea( CAS RN 570415-88-2), or
5-(2,6-difluoro-benzyloxymethyl)-5-methyl-3-(3-methy-thiophen-2-y)-4,5-dihydroisoxazole
(CAS RN 403640-27-7).
The mixing partners of the compound of formula (I) may also be in the form of
esters or salts, as mentioned e.g. in The Pesticide Manual, 13th Edition (BCPC), 2003.
The reference to acifluorfen-sodium also applies to acifluorfen, and the reference to
bensulfuron-methyl also applies to bensulfuron, etc.
The mixing ratio of the compound of formula (I) to the mixing partner (e.g. further
herbicide) is typically from 1: 300 to 300:l by weight or from 1: 100 to 100:l by weight;
or preferably from 1: 30 to 30:l by weight.
The mixtures can advantageously be used in the above-mentioned formulations
(in which case "active ingredient" relates to the respective mixture of compound of
formula (I) with the mixing partner).
The compounds of formula (I) according to the invention can also be used in
combination with one or more safeners. Likewise, mixtures of a compound of formula (I)
according to the invention with one or more further herbicides can also be used in
combination with one or more safeners. The term "safener" as used herein means a
chemical that when used in combination with a herbicide reduces the undesirable effects
of the herbicide on non-target plants, for example, typically a safener protects crop
plants from injury by herbicides, or minimizes such injury, but does not prevent the
herbicide from killing or inhibiting the growth of weeds.
The invention therefore provides a mixture (e.g. herbicidal composition, e.g.
liquid or solid), which comprises a herbicidally effective amount of a compound of
formula (I) and a safener.
The invention also provides a mixture (e.g. herbicidal composition, e.g. liquid or
solid), which comprises a herbicidally effective amount of a compound of formula (I), a
further herbicide as a mixture partner for the compound of formula (I), and a safener.
The safener can be AD-67 (1 I), benoxacor (63), cloquintocet-mexyl (163),
cyometrinil (GAS RN 78370-21-5), cyprosulfamide (CAS RN 221667-31-8), dichlormid
(231), dicyclonon (CAS RN 79260-71-2), fenchlorazole-ethyl (331), fenclorim (332),
flurazole (386), fluxofenim (399), furilazole (413) or the corresponding R isomer thereof,
isoxadifen-ethyl (478), mefenpyr-diethyl (506), 2-methoxy-N-[[4-
[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide(C AS RN 129531-12 -O),
naphthalic anhydride (CAS RN 81-84-5), N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyI)amino]benzenesulfonamide, or oxabetrinil (598).
In one particular embodiment, the safener is benoxacor, cloquintocet-mexyl,
mefenpyr-diethyl, cyprosulfamide or N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyI)amino]benzenesulfonamide.
The mixture with the safener can be applied to a crop of useful plants, for
example a perennial crop, such as citrus fruit, grapevines, nuts, oil palms, olives, pome
fruit, stone fruit or rubber; or an annual arable crop, such as a cereal (e.g. wheat, barley,
rye, or triticale, etc.), cotton, oilseed rape, maize (corn), rice, soybean, sugarbeet,
sugarcane, sunflowers, an ornamental or a vegetable.
The safeners of the compound of formula (I) may also be in the form of esters or
salts, as mentioned e.g. in The Pesticide Manual, 13th Edition (BCPC), 2003. The
reference to cloquintocet-mexyl also applies to cloquintocet, the reference to mefenpyrdiethyl
also applies to mefenpyr, and the reference to fenchlorazole-ethyl also applies to
fenchlorazole, etc.
Preferably, in the mixture, the ratio of the compound of formula (I) to the safener
is from 100:l to 1.10 by weight, especially from 20:l to 1.1 by weight.
The mixtures can advantageously be used in the above-mentioned formulations
(in which case "active ingredient" relates to the respective mixture of compound of
formula (I) with the safener). It is possible that the safener and a compound of formula
(I) and one or more additional herbicide(s), if any, are applied simultaneously. For
example, the safener, a compound of formula (I) and one or more additional
herbicide(s), if any, might be applied to the locus pre-emergence or might be applied to
the crop post-emergence. It is also possible that the safener and a compound of formula
(I) and one or more additional herbicide(s), if any, are applied sequentially. For example,
the safener might be applied before sowing the seeds as a seed treatment and a
compound of formula (I) and one or more additional herbicides, if any, might be applied
to the locus pre-emergence or might be applied to the crop post-emergence.
Preferred mixtures of a compound of formula (I) with further herbicides and
safeners include:
Mixtures of a compound of formula (I) with S-metolachlor and a safener,
particularly benoxacor.
Mixtures of a compound of formula (I) with S-metolachior and mesotrione and a
safener, particularly benoxacor.
Mixtures of a compound of formula (I) with isoxaflutole and a safener.
Mixtures of a compound of formula (I) with mesotrione and a safener, particularly
benoxacor.
Mixtures of a compound of formula (I) with sulcotrione and a safener.
Mixtures of a compound of formula (I) with a triazine and a safener.
Mixtures of a compound of formula (I) with a triazine and isoxaflutole and a
safener.
Mixtures of a compound of formula (I) with a triazine and mesotrione and a
safener.
Mixtures of a compound of formula (I) with a triazine and sulcotrione and a
safener.
Mixtures of a compound of formula (I) with glyphosate and a safener.
Mixtures of a compound of formula (I) with glyphosate and isoxaflutole and a
safener.
Mixtures of a compound of formula (I) with glyphosate and mesotrione and a
safener.
Mixtures of a compound of formula (I) with glyphosate and sulcotrione and a
safener.
Mixtures of a compound of formula (I) with glufosinate-ammonium and a safener.
Mixtures of a compound of formula (I) with glufosinate-ammonium and
isoxaflutole and asafener.
Mixtures of a compound of formula (I) with glufosinate-ammonium a d
mesotrione and a safener.
Mixtures of a compound of formula (I) with glufosinate-ammonium and
sulcotrione and a safener.
Mixtures of a compound of formula (I) with florasulam and a safener, particularly
cloquintocet-mexyl.
Mixtures of a compound of formula (I) with clodinafop-propargyl and a safener,
particularly cloquintocet-mexyl.
Mixtures of a compound of formula (I) with pinoxaden and a safener, particularly
cloquintocet-mexyl.
Mixtures of a compound of formula (I) with bromoxynii and a safener, particularly
cloquintocet-mexyl.
The following Examples further illustrate, but do not limit, the invention.
Abbreviations:
DMF dimethylformamide
LHMDS lithium hexamethyldisilazide
NMR nuclear magnetic resonance
LCMS liquid chromatography - mass spectrometry
GCMS gas chromatography - mass spectrometry
RT (in the context of LCMS or GCMS) retention time
RT (in the context of temperature) room temperature (ambient temperature),
which is usually about 18-25 "C.
Preparation Examples
The following abbreviations were used throughout this section: s = singlet; bs =
broad singlet; d = doublet; dd = double doublet; dt = double triplet; t = triplet, tt =triple
triplet, q = quartet, sept = septet; m = multiplet; Me = methyl; Et = ethyl; Pr = propyl; Bu
= butyl.
1. Reactions which are covered bv Scheme 2
Example 1. I:P reparation of 2-(2,4-Dichloro-ohen~lmethanesulfonvlamino)-nicotinica cid
methvl ester
The (2,4-dichloro-pheny1)-methanesulfonyl chloride (2.3989, Aldrich 734853) was
suspended in dichloromethane (21 ml) and methyl 2-aminonicotinate (1.278g, Aldrich
715107) was added followed by portion wise addition of pyridine (3.4ml). The reaction
mixture was heated at -40'C for 5 hours and left to cool. The reaction mixture was
diluted with dichloromethane and washed x3 with deionised water. The organic layer
was concentrated to leave an orange oil. The residue was purified by column
chromatography on silica gel (eluent: ethyl acetate I iso-hexane ratio 2:3) to give 2-(2,4-
Dichloro-phenylmethanesulfonylamino)-nicotinica cid methyl ester as a white crystalline
solid (2.0529). 1H-NMR (400 MHz, CDC13): 10.30 (s, IH), 8.58-8.59 (d, IH), 8.30-8.32
(d, IH), 7.41-7.46 (m, IH), 7.25-7.27 (m, IH), 7.08-7.11 (m, ZH), 5.12 (s, 2H), 3.94 (s,
3H) P P ~ .
Example 1.2: Preparation of 2-~~2.4-Dichloro-phenvlmethanesulfonvl)-(2.2-difluoroethyl)-
aminol-nicotinic acid methyl ester
To a solution of 2-(2,4-Dichloro-phenylmethanesulfonylamino)-nicotinica cid
methyl ester (507 mg) (Example 2.1) in acetonitrile (6.2ml) was added
diisopropylethylamine (0.27 ml). The mixture was stirred for 5 minutes at ambient
temperature before drop wise addition of a solution of 2,2-
difluoroethyltrifluoromethanesulfonate (603 mg) at ambient temperature. The reaction
mixture was stirred at ambient temperature overnight. The organic layer was
concentrated and the residue was purified by column chromatography on silica gel
(eluent: ethyl acetate I iso-hexane ratio 1 :2) to give 2-[(2,4-DichlorophenylmethanesulfonyI)-(
2,2-difluoro-ethyl)-amino]-nicotinic acid methyl ester as an
orange oil (470 mg). 1 H-NMR (400 MHz, CDC13): 8.55-8.56 (d, IH), 8.25-8.26 (d, 1 H),
7.45-7.47 (d, 1 H), 7.37-7.40 (m, 1 H), 7.25 (s, 1 H), 7.1 7-7.19 (d, 1 H), 5.94-6.24 (tt, 1 H),
4.53 (s, ZH), 4.20-4.28 (dt, ZH), 3.92 (s, 3H) ppm.
Example 1.3: Preparation of 3-(2.4-Dichloro-phenvl)-l-(2.2-difluoro-ethvl~-2.2-dioxo-1,2-
dihvdro-2-A-6-pvrido~2,3-cl[,l 2lthiazin-4-01 (Compound A1 of Table A)
0'
THF ,S=O CI
CI
F F
Sodium hexamethyldisilazide ("NaHMDS) (2.65 ml) (1M in tetrahydrofuran) was
added drop wise to a solution of 2-[(2,4-Dichloro-phenylmethanesulfonyl)-(2,2-difluoroethyl)-
amino]-nicotinic acid methyl ester (Example 2.2) (0.47 g) in tetrahydrofuran (17.7
ml) under a nitrogen atmosphere at ambient temperature. The reaction mixture was
partitioned between ethyl acetate and 2M hydrochloric acid. The phases were separated
and the organic phase was concentrated to give an orange oil which crystallized on
standing to give Compound No. A1 of Table A (467 mg). 1H-NMR (400 MHz, CDCI,):
8.65-8.67 (d, 1 H), 8.48-8.50 (d, 1 H), 7.58 (s, 1 H), 7.44-7.46 (d, 1 H), 7.35-7.38 (d, 1 H),
7.29-7.31 (m, 1 H), 6.10 (s, 1 H), 6.09-6.38 (tt, 1 H), 4.46-4.58 (m, 2H) ppm.
Example 1.4: Preparation of 2.2-Dimethvl-propionic acid 3-(2.4-dichloro-phenvl)-1-(2.2-
difluoro-ethyl)-2.2-dioxo-I .2-dihydro-2-A-6-pvrido[2,3-cl~l.21thiazin-4-vel ster (Compound
A2 of Table A)
t-BuCOCI,
pyridine
F F
Compound A1 of Table A (0.1 g) was dissolved in acetonitrile (1.8 ml) at ambient
temperature and N, N-dimethylaminopyridine (0.006 g) was added. 2,2-
Dimethylpropionyl chloride (0.065 ml) was added and the reaction mixture heated in a
microwave vial at 150% for 1500 seconds. The reaction mixture was concentrated and
the residue was purified by column chromatography on silica gel (eluent: ethyl acetate I
hexane I :I) to give 2,2-Dimethyl-propionic acid 3-(2,4-dichloro-phenyl)-I-(2.2-difluoroethyl)-
2,2-dioxo-I ,2-dihydro-2-A-6-pyrido[2,3-c][1 ,2]thiazin-4-yl ester as a colourless oil
which slowly solidified (52 mg). 1H-NMR (400 MHz, CDCI,): 8.55 (d, IH), 7.77-7.79 (d,
IH), 7.55 (s, IH), 7.45-7.47 (d, IH), 7.23-7.26 (m, IH), 7.35-7.37 (d, IH), 6.13-6.43 (tt,
1 H), 4.56-4.79 (m, ZH), 1.08 (s, 9H) ppm.
Table A:
Compounds of formula (A), where R3, R4 and R5 have the values as described in the
table below.
IH-NMR (400 MHz, CDC13
except where indicated;
chemical shifls in ppm)
~ .. ~
.-
2,4-
dichlorophenyldichlorophenyl-
..~ ........... ~ ~ . . . ~ ~ ~ ~~ ~, .~ R 5 . . ~ 1H-NMR (400 MHz, CDCI~
except where indicated;
chemical shifts in ppm)
.
HO- 8.65-8.67 (d, 1 H), 8.48-8.50 (d,
1 H), 7.58 (s, 1 H), 7.44-7.46 (d,
1 H), 7.35-7.38 (d, 1 H), 7.29-
7.31 (m,1H),6.10(s,1H),6.09-
6.38 (tt, IH), 4.46-4.58 (m, 2H)
t-Bu-(C0)O- 8.55 (d, IH), 7.77-7.79 (d, 1 H),
7.55 (s, 1 H), 7.45-7.47 (d, 1 H),
7.23-7.26 (m, 1 H), 7.35-7.37 (d,
IH), 6.13-6.43 (tt, IH), 4.56-
4.79 (m, 2H), 1.08 (s, 9H)
BIOLOGICAL EXAMPLES
Example B1 Herbicidal action post-emergence
Seeds of a variety of test species were sown in standard soil in pots. After 8 days
cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°C,
daylnight; 14 hours light; 65% humidity), the plants were sprayed with an aqueous spray
solution derived from the formulation of the technical active ingredient in acetone I water
(50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate,
CAS RN 9005-64-5). The test plants were then grown under controlled conditions in a
glasshouse (at 24116OC, daylnight; 14 hours light; 65% humidity) and watered twice
daily. After 13 days, the test was evaluated (10 = total damage to plant; 0 = no damage
to plant).
Table B1: Application ~ost-emerqence
Compound Rate SOLNl AMARE SETFA ECHCG IPOHE
SOLNl = Solanum nigrum; AMARE = Amaranthus retroflexus; SETFA = Setaria faberi;
ECHCG = Echinochloa crus-galli; IPOHE = lpomea hederaceae.

CLAIMS
1. A compound of formula (I)
wherein
A', A2, and A3 are independently C-R' or N, provided at least one of A', A2, and A3 is N;
each R' is independently hydrogen. Cl-C4alkyl, C1-C4 alkenyl, Cl-C4 alkynyl, C1-
C4haloalkyl, C3-C~cy~loalkyhla, lo, cyano, hydroxy, C1-C4alkoxy,C 02R2,C (0)R2
where R2 is hydrogen or C1-CG alkyl, C1-C4alkylthio, aryl or aryl substituted by
one to five RG groups which may be the same or different, or heteroaryl or
heteroaryl substituted by one to five RG groups which may be the same or
different;
R is hydrogen, OR5, thiol (HS-), C1-C3alkylthio-, C,fluoroalkylthio-, Cl-C3alkyl-S(0)-,
C,fluoroalkyl-S(0)-, C1-C3alkyl-S(0)2-, C,fluoroalkyl-S(O),-, H2N-S(0)2-, C1-
C4alkyl-NH-S(0)2-,( C1-C3alkyl)2N-S(0)2-h, alo, cyano, C1-C4alkyl,C 1-C2haloalkyol r Cl-
C4alkoxy and NR'32 wherein each R13 is independently selected from the group
hydrogen, C1.4alkyl, SO~R", phenyl and phenyl which is mono or poly-substituted with
R7:
R3 is hydrogen, C1-Cloalkyl, Cl-C4haloalkyl, C2-Cloalkenyl, C2-C4haloalkenyl. C2-
Cloalkynyl, C2-C4haloalkynyl,C 3-Clocycloalkyl, C3-Clocycloalkyl-Cl-C~alkyl-C, l-
Cloalk0~y-C1-C6alkyl-C, 1-Clocyanoalkyl-, C1-C,oalkoxycarbonyl-Ci-~Ga~kyN~-C-, l-
C3alkyl-aminocarbonyl-C,-C,alkyl-, N,N-di-(Cl-C3alkyl)-aminocarbonyl-C,-C,aky aryl-
C1-C~alkylo-r aryl-C,-CGalkyl-w herein the aryl moiety is substituted by one to three R7,
which may be the same or different, or heterocyclyl-C1-C~alkyl-w, herein the heterocyclyl
moiety is substituted by one to three R7groups, which may be the same or different; or
R3 is R4 of sub-formula (a);
R4 is of sub-formula (a) or (b):
wherein, in sub-formula (a):
R4=,R ~R4~', R,~ ~a nd R4ea re each independently hydrogen, halogen, cyano, C,-C4alkyl,
C,-C2fluoroalkyl, C1-C3alkoxy-C,-C~alkyl-, Clfluoroalkoxy-C,-C2alkyl-,
MeOCH2CH20CH2-, C3-C6cycloalkyl, hydroxy, Cl-C4alkoxy, Cl-C2fluoroalkoxy, thiol (HS-
), Cj-C3alkylthio-, C,fluoroalkylthio-, Cl-C3alkyl-S(0)-. Clfluoroalkyl-S(0)-, C,-C3alkyl-
S(0)2-, C,fluoroalkyl-S(O)Z-, HZN-S(O)Z-C, ,-C4alkyl-NH-S(0)2-, (C1-C3alkyl)2N-S(0)2-- ,
S(0)2-OC,-C4alkyl, -S(0)2-OC,-C2fluoroaIkyl, C1-C4alkyl-C(0)-, H-C(0)-, C,-C3alkoxy-
C(0)-, HO-C(0)-, H2N-C(0)-, Cl-C4alkyl-NH-C(0)-, (C,-C3alkyl)2N-C(0)-. (I-pyrrolidinyl).
C(0)-, (I-piperidiny1)-C(0)-, amino, C1-C4alkyl-NH-, (Cl-C3alkyl)2N-, I-pyrrolidinyl,
1-piperidinyl, C1-C4alkyl-C(0)-NH-, H-C(0)-NH-, Cl-C,alkyl-C(0)-N(Cl-C3alkyl)-,
2-0x0-I-pyrrolidinyl, 2-0x0-I-piperidinyl, C,-C3alkyl-S(0)2-NH-, Cl-C3alkyl-S(0)2-N(C1-
C3alkyl)-, phenyl or phenyl substituted by one, two or three of R7, or phenoxy or phenoxy
substituted by one, two or three of R7;
and wherein, in sub-formula (b):
A5 is N or cR4', A6 is N or CR4g,A 7 is N or C R ~A~8 i.s N or C R ~a~nd, Asis N or cR4',
provided that one or two of A5, A ~A,7 , A8 and A9 are nitrogen and the remaining ones of
A5, A6, A7, A8 and A9 are not nitrogen;
R4', R4g,R 4h,R ~~a nd R~~a re each independently hydrogen, halogen, Cl-C4alkyl, C1-
C2fluoroalkyl, C,-C3aikoxy-methyl-, Clfluoroalkoxy-methyl-, MeOCH2CH20CH2-C, 3-
C,cycloalkyl, hydroxy (inclusive of any tautomer thereof), C1-C4alkoxy, C1-
C2fluoroalkoxy, C,-C4alkyl-C(0)-, H-C(0)-, C1-C3alkoxy-C(0)-, HO-C(0)-, H2N-C(0)-, C1-
C4alkyl-NH-C(0)-, (C,-C3alkyl)2N-C(0)-, (I-pyrrolidiny1)-C(0)-, (I-piperidiny1)-C(0)-,
amino, C1-C4alkyl-NH-, (C,-C3alkyl)2N-, I-pyrrolidinyl, I-piperidinyl, C1-C4alkyl-C(0)-NH-,
H-C(0)-NH-, C1-C3alkyl-C(0)-N(C,-C3alkyl)-, 2-0x0-I-pyrrolidinyl, 2-0x0-I-piperidinyl,
phenyl or phenyl substituted by one, two or three of R8, or phenoxy or phenoxy
substituted by one, two or three of R8; or
R4' together with R4' may form a pyridine ring which is mono or poly-substituted with R4g
as defined above; or
R~~ together with R4' may form a five to ten membered saturated or partially unsaturated
mono- or bicyclic ring containing 1 to 3 heteroatoms selected from the group consisting
of N, S and 0 which may be unsubstituted or mono or poly-substituted with R4g as
defined above; or
R5 is hydroxy, R9-OXY-R, '~-C(O)-O-,C 1-Cloalkyl-S(0)20-, Clfluoroalkyl-S(0)20-,
C~chloroalkyl-S(O),O-, phenyl-S(O),O- or (4-methyl-phenyl)-S(0)20-;
each R6 and each R7 are independently halo, cyano, nitro, C1-Cloalkyl, Cl-C,haloalkyl,
C2-Cioalkenyl, C2-Cloalkynyl, hydroxy, C1-Cloalkoxy, C,-C4haloalkoxy, C,-C,oalkoxy-C,-
C4alkyl-, C3-C7cycloalkyl, C3-C7cycloalkoxy, C3-C,cycloalkyl-Cl-C4alkyl-, C3-C7cycloalkyi-
C1-C4alkoxy-, C,-C6alkylcarbonyl-, formyl, C1-C4alkoxycarbonyl-, C1-C4alkylcarbonyloxy-,
C1-Cloalkylthio-, Cl-C,haloalkylthio-, Cl-Cloalkylsulfinyl-, Cl-C4haloalkylsulfinyl-, C1-
Cloalkylsulfonyl-, Cl-C4haloalkylsulfonyl-, amino, C1-Cloalkylamino-, di-Cl-Cloalkylamino-
, C1-Cioalkylcarbonylamino-, aryl or aryl substituted by one to three R", which may be
the same or different, heteroaryl or heteroaryl substituted by one to three R", which may
be the same or different, aryl-Cl-C4alkyl- or aryl-Cl-C4alkyl- wherein the aryl moiety is
substituted by one to three R", which may be the same or different, heteroaryl-C1-
C4alkyl- or heteroaryl-Cl-C,alkyI- wherein the heteroaryl moiety is substituted by one to
three R", which may be the same or different, aryloxy- or aryloxy- substituted by one to
three R", which may be the same or different, heteroaryloxy- or heteroaryloxysubstituted
by one to three R", which may be the same or different, arylthio- or arylthiosubstituted
by one to three R", which may be the same or different, or heteroarylthio- or
heteroarylthio- substituted by one to three R", which may be the same or different;
each R8 is independently, fluorine, chlorine, C1-C2alkyl, Clfluoroalkyl, Cl-C2alkoxy or
Clfluoroalkoxy;
R9 is C,-Cloalkyl, Cl-C,fluoroalkyl, C2-Cloalkenyl, C2-C,,alkynyl, C3-C8cycloalkyl, C3-
C8~y~l0alkyl-C1-C4alkyCl-,, -C4alkoxy-CH2CH2-, C1-C4alkoxy-CH2CH2CH2p-,h enyl-C,-
C4alkyl-, or phenyl-C1-C4alkyl- wherein the phenyl moiety is substituted by one, two or
three R";
R" is C1-Cl0alkyl, Cl-C4fluoroalkyl, C2-C,oalkenyl, C2-C,oalkynyl, C3-C8cycloalkyl, C,-
C8cycloalkyl-C,-C4alkyl-, C,-C4alkoxy-C1-C4alkyl-, phenyl, phenyl substituted by one, two
or three R", phenyl-C1-C4alkyl-o, r phenyl-C1-C4alkyl-w herein the phenyl moiety is
substituted by one, two or three R";
each R1 1 i- s i.n dependently halo, Cl-C4alkyl, C1 C~fluoroalkyl,C ,-C4alkoxy, C1 -
C2fluoroalkoxy, phenyl or phenyl substituted with R ~ ;
each R1 2I.S .in dependently halo, cyano, nitro, C1-C~alkylC, 1-C~haloalkyolr Cl-CGalkoxy;
or a salt or N-oxide thereof
2. A compound of formula (I) according to claim 1 wherein up to two of A' and A'
are N.
3. A compound of formula (I) according to claim 1 or 2 wherein R' is independently
hydrogen, Cl-C4alkyl, Cl-C4haloalkyl, halo, cyano, hydroxyl, C1-C4alkoxy,C O ~ Ror ~
C(0)R2.
4. A compound of formula (I) according to any preceding claim wherein R3 is
hydrogen, C1-C4alkyl, C1-C4haloalkyl, CZ-C4alkenyl, C2-C4haloalkenyl, Cz-C4alkynyl, C,-
Cloalkoxy-C1-C8alkyl- or C2-C4haloalkynyl.
5. A compound of formula (I) according to any preceding claim wherein R is
hydrogen, OR^, thiol (HS-), C,.,alkylthio, halo, cyano or NR132.
6. A compound of formula (I) according to any preceding claim wherein R4 is sub
formula (a).
7. A compound of formula (I) according to any preceding claim wherein R4a, R ~ ~ ,
R4', R~~ and R4e are each independently selected from hydrogen, halogen, Cl-C4alkyl,
Clfluoroalkyl, methoxymethyl-, MeOCH2CH20CH2-, C3-C5cycloalkyl, C1-C,alkoxy,
Clfluoroalkoxy, C1-C3alkyl-S(0)z-H, 2N-S(O),-, C,-C3alkyl-NH-S(0)2-, (C1-C3alkyl)2NS(
O),-, ), phenyl or phenyl substituted by one or two of R7, wherein each R',
independently of any other R', is fluorine, chlorine, methyl, C,fluoroalkyl, methoxy or
C,fluoroalkoxy.
8. A compound of formula (I) according to any preceding claim wherein R4 is
selected from 2-trifluoromethyl-phenyl-; 2-chloro-phenyl-; 2-bromo-phenyl-; 2-methylphenyl-;
2-methoxy-phenyl-; 2,4-difluoro-phenyl-; 2,6-dichloro-phenyl-; 2,3-dichloro-6-
fluoro-phenyl-; 2-chloro-3,6-difluoro-phenyl-; 3-bromo-2-chloro-6-fluoro-phenyl-; 2,3,6-
trichloro-phenyl-; 2-chloro-5-trifluoromethyl-phenyl-; 2-chloro-6-trifluoromethyl-phenyl-;
2,5-bis-(trifluoromethyl)-phenyl-; 2-bromo-5-chloro-phenyl-; 4-bromo-2-trifluoromethylphenyl-;
4-chloro-2-methylsulfonyl-phenyl-; 4-chloro-2-trifluoromethyl-phenyl-; 5-chloro-
2-trifluoromethyl-phenyl-; 3,5-difluoro-2-trifluoromethyl-phenyl-; 2-ethyl-4-(4'-chlorophenyl)-
phenyl-; 2,4,6-trimethyl-phenyl-; 4-chloro-phenyl-; and 3-trifluoromethyl-phenyl-;
4-fluoro-2-trifluoromethyl-phenyl-; 5-fluoro-2-trifluoromethyl-phenyl-; 2,4-dichloro-phenyl-
; and 2-chloro-3,6-difluoro-phenyl-.
9. A compound of formula (I) according to any preceding claim wherein R~ is
hydroxyl, ~'-oxy-o r R1O-C(0)-O-w, here RO' is C,-C~alkyl.
10. A herbicidal composition which comprises a herbicidally effective amount of a
compound of formula (I) as defined in any of claims 1 to 11 in combination with at least
one formulation carrier, andlor solvent.
11. A herbicidal composition according to claim 12 which comprises at least one
further herbicide, and optionally at least one safener.
12. A herbicidal composition according to claim 13, wherein the at least one further
herbicide is a HPPD inhibitor.
13. A herbicidal composition according to claim 14, wherein the HPPD inhibitor is
selected from the group consisting of pyrazolynate, benzofenap, isoxachlortole,
tefuryltrione, pyrazoxyfen, benzobicyclon, isoxaflutole (479), mesotrione (515),
pyrasulfotole, sulcotrione (747), tembotrione, topramezone, bicyclopyrone, or 4-hydroxy-
3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.l]oct-3-en-2-
one (CAS RN 894355-80-7)).
14. A method of controlling unwanted plants which comprises applying to the plants
or to the locus thereof a herbicidally effective amount of a compound of formula (I) as
defined in any one of claims 1 to 11, or a herbicidal composition as defined in any one of
claims 12 to 15.
15. Process for the preparation of compounds of formula (I) as defined in claim 1 in
which R3 is other than hydrogen and R5 is hydroxy, which comprises reacting a
compound of formula (3)
R
wherein A,, A2, A3 and R are as defined in claim 1, R2 is hydrogen or Cl-C,-alkyl and X
is a leaving group such as halogen; with a compound of formula (2)
R4
($0
R\~/s,,
H 0 (2)
wherein X is halogen and R4 is as defined in claim 1; to form the compound of formula
(1) or a compound of formula (K)
R
which is subsequently converted to a compound of formula (1) as defined herein.
16. Process for the preparation of compounds of formula (I) as defined in claim 1 in which
R3 is hydrogen and R5 is hydroxy, which comprises treating a compound of formula (J)
R
wherein A,, A*. A, R and R4 are as defined in claim 1 and R2 is hydrogen or C,-CB-alkyl
and X is a leaving group; with a base optionally in the presence of heat or microwave
heat.
17. Process for the preparation of compounds of formula (I) as defined in claim 1 in
which R5 is R~~-C(O)-wOh-i ch comprises reacting a compound of formula (D)
R OH
with an acid chloride of formula R'O-COCI or an acid anhydride of formula (R'~CO)~O
wherein Ria is as defined in claim 1.
18. Process for the preparation of compounds of formula (I) as defined in claim 1 in
which R5 is RIO-C(0)-0- and R3 is not hydrogen which comprises reacting a compound
of formula (I) in which R5 is RIO-C(0)-0- and R3 is hydrogen with a compound of formula
R~LGwh ere LG is a leaving group, in the presence of a base and a suitable solvent.
19. Process for the preparation of compounds of formula (I) as defined in claim 1 in
which R5 is -0-R9 and R3 is not hydrogen which comprises reacting a compound of
formula (I) in which R5 is hydroxy and R3 is not hydrogen with a compound of formula
RgLG where LG is a leaving group, in the presence of a base and a suitable solvent,.
20. Process for the preparation of compounds of formula (I) as defined in claim 1 in
which R5 is hydroxy and R3 is not hydrogen which comprises treating a compound of
formula (I) in which R5 is R1cC(0)-0- and R3 is not hydrogen with a base in a suitable
solvent.
21. Process for the preparation of compounds of formula (1) as claimed in any of
claims 17 to 22 which comprises the additional step of converting the compound of
formula (I) to a salt or N-oxide thereof.
22. A compound of formula
wherein Al, A2, A3, R, R3 and R4 are as defined in claim 1 and R2 is hydrogen or Cl-C,-
alkyl.